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Refining-Pelrochemicals-Chemicals-Engineering

F U r - M M i G N iNSU.Srii F.
irp •

T R A I N I N G

TECHNIP BENELUX B.V.

PETROCHEMICALS
Olefins - Aromatics & Polyolefins

-

SUMMARY OF TECHNICAL DOCUMENTATION

-

MAIN ECONOMIC DATA IN PETROCHEMISTRY
FAMILIES OF HYDROCARBONS AND MAJOR PETROCHEMICAL DERIVATIVES
FAMILIES OF HYDROCARBONS AND MAJOR PETROCHEMICAL DERIVATIVES - Figures

STEAMCRACKING - Figures
AN EXAMPLE OF A NAPHTHA CRACKER UNIT
CONTINUOUS DISTILLATION
IMPLEMENTATION OF EXTRACTIVE DISTILLATION
VARIOUS ROUTES FOR C CUT UPGRADING
4

NATURE OF AROMATIC HYDROCARBONS, SOURCES AND ASSOCIATED PROCESSES
NATURE OF AROMATIC HYDROCARBONS, SOURCES AND ASSOCIATED PROCESSES -

STYRENE MONOMER PRODUCTION
ADDITION POLYMERIZATION - Techniques and main characteristics
VARIOUS POLYETHYLENE - MANUFACTURING PROCESSES
VARIOUS PROCESSES FOR MANUFACTURING POLYPROPYLENE

RPC/PETRO-E_G_A - 04685. B. A - Rev. 0
V

© 2008 ENSPM Formation Industrie - IFP Training

05/06/2008
)

Refining-Petrochemicals-Chemicals-Engineering

11 /04/2008 - V
RPC / PETRO-E_G_A

FORMATION INDUSTRIE
IFP

T R A I N I N G

TECHNIP BENELUX B.V.

PETROCHEMICALS
Olefins - Aromatics & Polyolefins
DURATION 3 DAYS
WHO SHOULD ATTEND?
Persons working in the petroleum and petrochemical sectors seeking an introduction to the petrochemical aspects of olefins,
aromatics and polyolefins.

OBJECTIVES
On completion of the course, participants:
- are familiar with the sources, outlets and main industrial uses of olefinic and aromatic compounds
- have a grasp of the functions and main characteristics of the petrochemical processes and units currently used in the
industry to produce, separate and purify the compounds concerned
- get an overview of PE & PP processes

C O U R S E CONTENT

STEAM CRACKING AND TREATMENT OF THE CUTS PRODUCED

1.75 days

Pyrolysis
Analysis of the hydrocarbon feedstock for steam cracking process.
Implementation: furnace, quench, primary separation.
Yields, operating variables affecting treatment severity, influence of the nature of the feed.
Compression and purification of the cracked gases
Implementation of compression.
H2S and CO2 removal by alkaline washing.
Drying of gases by adsorption.
Cooling: propylene and ethylene chilling cycles, cold box.
Separation and treatment of steam cracker effluents
Steam cracker effluent separation train, main characteristics of the cuts produced, specific impurities
and particular constraints; acetylene removal from the C2 cut, selective hydrogenation of MAC and
propadiene in the C3 cut.
Treatment of the C4 cut, 1,3- butadiene recovery from isobutene and 1- butene.
Steam cracked gasoline treatment for the production of motor fuels and benzene.
Comparison between ethane cracker and naphtha cracker processes

PRODUCTION OF AROMATICS

0.75 day

Catalytic reforming and BTX production
Analysis of the process, the catalyst, yields, operating variables.
Characteristics of BTX effluents - Influence of the nature and cut points of feeds.
Aromatics-non-aromatics separation processes
Liquid-liquid extraction, extractive distillation.
Associated processes
Hydrodealkylation, disproportionation, isomerization.
Aromatic separation processes
Distillation, adsorption on solid: application to xylene separation.
Styrene production
Benzene alkylation, ethylbenzene dehydrogenation - Manufacturing conditions.

IMPLEMENTATION OF POLYMERIZATION - MAIN POLYETHYLENE
AND POLYPROPYLENE PROCESSES
Techniques implemented in polymers production: solution, bulk, emulsion, suspension or slurry, gas
phase
Advantages and drawbacks of these techniques, consequences for process implementation
Main processes involved in production of polyethylene and polypropylene. Basic schemes and average
operating conditions. Influence of operating parameters (temperature, pressure, reactants proportion) on
product quality

0.5 day

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Refining-Petrochemicals-Chemicals-Engineering

FORMATION INDUSTRIE
IFP

T R A I N I N G

TECHNIP BENELUX B.V.

PETROCHEMICALS
Olefins - Aromatics & Polyolefins

— SUMMARY OF TECHNICAL DOCUMENTATION —

MAIN ECONOMIC DATA IN PETROCHEMISTRY
FAMILIES OF HYDROCARBONS AND MAJOR PETROCHEMICAL DERIVATIVES
FAMILIES OF HYDROCARBONS AND MAJOR PETROCHEMICAL DERIVATIVES - Figures
STEAMCRACKING
STEAMCRACKING - Figures
AN EXAMPLE OF A NAPHTHA CRACKER UNIT
CONTINUOUS DISTILLATION
IMPLEMENTATION OF EXTRACTIVE DISTILLATION
VARIOUS ROUTES FOR C CUT UPGRADING
4

NATURE OF AROMATIC HYDROCARBONS, SOURCES AND ASSOCIATED PROCESSES
NATURE OF AROMATIC HYDROCARBONS, SOURCES AND ASSOCIATED PROCESSES Figures
STYRENE MONOMER PRODUCTION
ADDITION POLYMERIZATION - Techniques and main characteristics
VARIOUS POLYETHYLENE - MANUFACTURING PROCESSES
VARIOUS PROCESSES FOR MANUFACTURING POLYPROPYLENE

RPC/PETRO-E_G A - 04685_B_A - Rev. 0
© 2008 ENSPM Formation Industrie - IFP Training

05/06/2008

IFP

Rofipinq-Potrochemicals-Chemicals-Enqineermq

CN N U I S I W F
TRAINING

°

3

3

MAIN ECONOMIC DATA IN P E T R O C H E M I S T R Y

ETHYLENE - PROPYLENE: domestic, European and world production

figure n°1

BENZENE - TOLUENE: domestic, European and world production

figure n°2

PARAXYLENE - ORTHOXYLENE: domestic. European
and world production

figure n°3

World petrochemical production report

figure n°4

Western European ethylene consumption by derivatives

figure n°5

Western European propylene consumption by derivatives

figure n°6

Western European benzene consumption by derivatives

figure n°7

Western European capacities and production data of main petrochemical products

figure n°8

European ethylene production capacities

figure n°9

Domestic steamcrackers location

figure n°10

End uses for steam cracking products based on world repartition

figure n°11

Location of European crackers

figure n"12

Location of crackers in BENELUX Region

figure n°13

Location of CIS crackers

figure n°14

European olefins pipelines

figure n°15

05/06/2008

I

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Figure n°1 -

FORMATION INDUSTRIE
IFP

TRAINING.

'ETHYLENE
GROWTH FORECAST

Mt
87

WORLD PRODUCTION (2003)

— > 2010
4.5%/y

[CAPACITY]

[100.9]

EUROPEAN PRODUCTION (2005)

m

21.6

— > years to come
1.6%/y

DOMESTIC PRODUCTION (2005)

3.046

PROPYLENE
GROWTH FORECAST

Mt
WORLD PRODUCTION (2002)

56

- - > 2006
5.2%/y

EUROPEAN PRODUCTION (2005)

15.53

— > 2009
2.2%/y

DOMESTIC PRODUCTION (2005)

2.302

00037 A_A

© 2008 ENSPM Formation Industrie - IFP Training

IFP

TRAINING

BENZENE
GROWTH FORECAST

Mt
WORLD PRODUCTION (2002)

33

- - > 2007
2.8-4%/y

[CAPACITY]

[39]

EUROPEAN PRODUCTION (2005)

8.407

- - > 2007
3.1 %/y

DOMESTIC PRODUCTION (2005)

0.78

TOLUENE
Mt
WORLD PRODUCTION (2002)

13

GROWTH FORECAST
- - > 2007
2.6 - 3.5%/y

[CAPACITY]

[19]

EUROPEAN PRODUCTION (2005)

2.140

DOMESTIC PRODUCTION (2005)

0.058

( 00037JU\
© 2008 ENSPM Formation Industrie - IFP Training

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FORMATION INDUSTRIE
IFP

*

TRAINING

PARAXYLENE
GROWTH FORECAST

Mt
WORLD PRODUCTION (2002)

17.5

- - > 2005
6%/y

EUROPEAN PRODUCTION (2004)

2.137

DOMESTJCPRODUCTION (2002)

0.12

ORTHOXYLENE
Mt

^

EUROPEAN PRODUCTION (2004)

0.492

DOMESTIC PRODUCTION (2002)

0.08

00037_A_A

© 2008 ENSPM Formation Industrie - IFP Training

'

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^

Figure n°4 -

FORMATION INDUSTRIE
IFP

a

TRAINING

2005 WORLD PETROCHEMICAL PRODUCTION REPORT

PRODUCTION
(Mt)

ASIA

EUROPE

NORTH
AMERICA

SOUTH
AMERICA

ETHYLENE

15.824

21.600

28.688

3.853

PROPYLENE

11.258

15.406

16.608

1,908

BENZENE

8.726

8.425

7.647

1.118

Source: International Petrochemical Information Forum

00037 A_A
V

-

© 2008 ENSPM Formation Industrie - IFP Training

'

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FORMATION INDUSTRIE
IFP

TRAINING

WESTERN EUROPEAN ETHYLENE CONSUMPTION
BY DERIVATIVES, 2005

— Figure 5 —

HDPE
7>
L D P E

Ethylene dichloride (EDC)

25

r

20
Ethylene oxide (EO)
15

Vinyl acetate and others

Ethylbenzene (EB)

23,8°/!

10
Acetaldehyde
m

Ethanol

'1.2%'.-

© 2008 ENSPM Formation Industrie - IFP Training

enspm
FORMATION INDUSTRIE
IFP

TRAINING

WESTERN EUROPEAN PROPYLENE CONSUMPTION
BY DERIVATIVES, 2005

— Figure 6 —

60

Polypropylene

(_

/

1/

Others
50

Propylene oxide (PO)
40

7

-3

Cumene

30

57,2%

Acrylonitrile (AN)
20

OXO Alcohols

10

Isopropanol
6.8%
Itt?

11.6%

Hill?

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

/

1

o

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FORMATION INDUSTRIE
IFP

WESTERN EUROPEAN BENZENE CONSUMPTION

TRAINING

BY DERIVATIVES, 2005

— Figure 7 —

60

Ethylbenzene (EB)
Cumene

50

/

7\

Nitrobenzene
Cyclohexane

40
Alkylbenzene
30
Others

49,8%

20

23,3%

10
1,6%

nil

i l l ™

© 2008 ENSPM Formation Industrie - IFP Training

- Figure n°8-1 FORMATION INDUSTRIE
IFP

TRAINING

WESTERN EUROPEAN CAPACITIES AND PRODUCTION DATA
OF MAIN PETROCHEMICAL PRODUCTS ( Mt)
2001

2002

2003

2004

2005

capacity
production

22.126
19.624

23.166
20.159

23.328
20.685

23.759
21.408

23.969
21.600

capacity
production

5.839
4.680

5.905
4.730

5.905
4.595

5.815
4.567

5.780
4.520

capacity
production

2.935
2.235

2.935
2.187

3.294
2.469

3.299
2.587

3.319
2.596

capacity
production

5.600
4.570

5.885
4.685

5.897
4.840

6.367
5.086

6.042
5.110

capacity
production

6.487
5.427

6.312
5.458

6.697
5.793

7.292
6.105

7.292
6.025

ETHYLENE

LDPE

LLDPE

HDPE

ETHYLBENZENE

STYRENE

^ ^ ^ ^ ^ ^ ^ ^
production

4 965

5.19

5.500

5.510

2.690
2.505

2.705
2.581

2.960
2.750

3.033
2.800

ETHYLENE OXIDE
capacity
production

2.770
2.320

ETHYLENE GLYCOL

^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^
WmWmmLWmmWU
ETHYLENE DICHLORIDE
capacity
production

12.451
9.557

12.685
10

1.260

1.410

1.380

12.725
9.893

13.104
10.241

13.116
10.199

00037_A_A
V

-

© 2008 ENSPM Formation Industrie - IFP Training

J

- Figure n°8-2FORMATION INDUSTRIE
IFP

*

TRAINING

2001

2002

2003

2004

2005

VINYL CHLORIDE MONOMER

^ ^ ^ ^ ^ ^ ^ ^
5 622

6.870
6.043

5.911

PROPYLENE
capacity
production

16.184
13.420

16.729
14.098

17.200
14.666

17.597
15.187

17.834
15.532

capacity
production

9.227
7.575

9.407
8.188

9.992
8.901

10.097
9.237

10.247
9.368

capacity
production

1.174
1.033

1.164
0.954

1.025
0.850

0.935
0.790

0.935
0.830

capacity
production

3.035
2.460

3.080
2.370

3.350
2.855

3.350
3.020

3.415
3.040

2.100

2.250

2.375

POLYPROPYLENE

ACRYLONITRILE

CUMENE

PHENOL
2.436
production
PROPYLENE OXIDE
capacity
production

2.075
1.837

2.100
1.950

2.127
1.978

2.367
2.292

2.387
2.338

capacity
production

2.445
2.097

2.492
1.992

2.474
2.024

2.459
2.130

2.474
2.221

capacity
production

8.935
7.530

9.040
7.562

9.540
7.949

9.903
8.464

9.784
8.480

capacity
production

1.345
0.918

1.375
1.078

1.405
1.080

1.406
1.090

1.411
1.065

capacity
production

2.623
2.120

2.518
2.175

2.578
2.185

2.538
2.140

2.538
2.080

BUTADIENE

BENZENE

CYCLOHEXANE

TOLUENE

^

1

© 2008 ENSPM Formation Industrie - IFP Training

1

^

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^

FORMATION INDUSTRIE
IFP

TRAINING

- Figure n°8-3 -

2001

2002

2003

2004

2005

0.647
0.456

0.647
0.484

0.647
0.486

0.667
0.492

0.670
0.484

ORTHOXYLENE
capacity
production
PrlTALiC ANHYDRID
capacity

^ ^ ^ ^ ^ ^ ^ ^

^ ^ ^ ^ ^ ^ ^ ^
0.680

0.690

0.695

0.630

2.260
1.874

2.345
2.080

2.373
2.137

2.444
2.115

2.170

2.855
2.431

2.955
2.620

3.005
2,783

0.890

0.960

0.990
0.885

0.990
0.888

PARAXYLENE
capacity
production

2.235
1.851

TEREFHTALIC ACID

^ ^ ^ ^ ^ ^ ^ ^
DIMETHVL TEREPnTALATE
capacity

00037_A_A

^

© 2 0 0 8 ENSPM Formation Industrie-IFP Training

J

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FORMATION INDUSTRIE
IFP

TRAINING

EUROPEAN ETHYLENE PRODUCTION CAPACITIES

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

DOMESTIC STEAM C R A C K E R S
LOCATION

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FORMATION INDUSTRIE
IFP

a

— Figure 10 —

TRAINING

DUNKERQUE

STEAM C R A C K E R S CAPACITIES
1/01/04
Location (compagny)

Capacity in 10001
of ethylene/year

Main feeds

CARUNG-TOTAL PETROCHEMICALS F

570

GPL-naphtha

DUNKERQUE-POLIMERIEUROPA

380

GPL - naphtha

PORT JEROME-EXXON MOBIL

425

GPL-naphtha-distillate

GONFREVILLE-ATOFINA

500

GPL - naphtha

LACQ-TOTAL PETROCHEMICALS F

75

Ethane

FEYZIN-AP. Feyzin (57,5% TPF - 42,5% Solvay)

250

GPL-naphtha

LAVERA-NAPHTACHIMIE (50% TPF - 50% BP)

740

GPL-naphtha

BERRE-BASELL

465

GPL - naphtha - diesel

TOTAL:

3405

A 5 y e a r s : + 230

© 2008 ENSPM Formation Industrie - IFP Training

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FORMATION INDUSTRIE
IFP

END U S E S FOR STEAM CRACKING PRODUCTS BASED ON WORLD REPARTITION

TRAINING

•Figure 11 —

— Figures correspond to 450,000 t/year of ethylene production —

POLYETHYLENES (245)
ETHYLENE (450)
VINYL CHLORIDE
Stream in 1000 t/year

>• PVC

ETHYLBENZENE -

(w)
POLYSTYRENES

STYRENE (JM5)

STYRENE-BUTADIENE RUBBER

ETHYLENE OXIDE

OTHERS
POLYPROPYLENES
PROPYLENE (220)

H2 +

ACRYLONITRILE

PLASTICS ABS
(J36

ACRYLIC FIBERS

ALCOHOLS O X O ( 2 3 )

Fuel Gas

OTHERS

PROPYLENE OXIDE
CUMENE (44)

NAPHTHA

PHENOL


ACETONE

STEAMCRACKING

STYRENE-BUTADIENE RUBBER
BUTADIENE RUBBER

BUTADIENE ( 5 5 )
Pyrolysis
fuel

C CUT
4

(J25)

BENZENE
FROM OTHERS
UNITS

OTHERS

BUTADIENE
EXTRACTION

ISOBUTENE (J33)

C CUT
4

-+Q

Raffinate 1

ISOBUTENE
RECOVERY

OTHERS BUTENES ( 2 6 )
CUT
Raffinate 2

BENZENE
GASOLINE CUT

(305)

OTHERS BUTENES
RECOVERY

C

4

(OTHERS)

QTJ

CYCLOHEXANE
BENZENE
EXTRACTION
OTHERS END USES

BENZENE FREE
GASOLINE CUT

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

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FOBUATION IN

IFP • TRAINING

— Figure 12 —

LOCATIONS OF EUROPEAN CRACKERS

NORWAY

Frontier

o Relevant cities



*

*•
S

Crude oil pipeline
Ethylene pipehne
Propylene pipeline
Under construction
Refinery
Refinery + Steam craker
Refinery + F C C
Steam craker
Ethylene terminal
Consumer

Cnxlenbay ;

IKELANO

monS
M*™^

-

USITHJ
NETHERLANDS

fr

fcf> Courowe

,-f i 4

LUXEysoURG'

..

....
AN3

,
YUGOSLAVIA

» So"*
, Pontano di Grano

i

*-

- •

fcJLGA«IA

*

fiillllfP^lll!

. Pnolo

*

CEFIC document
© 2008 ENSPM Formation Industrie - IFP Training

e n s p m
FORMATION INDUSTRIE
IFP

TRAINING

LOCATIONS OF C R A K E R S IN THE B E N E L U X REGION

o The Hague

— Figure 13-

NETHERLANDS

Rotterdam

N o r t h Sea

Marl
.1

# Pernis
o * Moerdijk

Rheinberg

Gelsenkirchen

Duisburg
Flushing

GERMANY
Temeuzenoi

p * Antwerp
_ra Meerhout

o -k Dunkirk
o Ghent

Tefcserjdc-rloo •"

Berinqen

Leverkusen
— : _ i p * Cologne
Geleen
Bonn o

\

o Brussels

CLO-ft Wesselina

B E \ 'G I U M
o Liege
n Fcluy
Jemoppefr

Frankfurti

FRANCE

LUXEMBOURG
o Luxembourg

Ludwigshafenogj
* Karlsruhe

—.... Frontier
o




Relevant cities
Major crude oil pipeline
Ethylene pipeline
Propylene pipeline
Propylene pipeline in study
Refinery
Olefins consumers
Refinery + olefins producer
Steam craker

CEFIC document

© 2008 ENSPM Formation Industrie - IFP Training

enspm
FOBHATION iwou>mte
IFP •

TRAINING

LOCATIONS OF CIS CRACKERS

-Figure 14-

enspm
— Figure 15 -

EUROPEAN OLEFINS PIPELINES

I F P • THAININQ

Frontier
Relevant cities
— Ethylene pipeline
Propylene pipe'me
Refinery + Steam cracker
Steam cracker
• Ethylene terminal
e Consumer
o

"liOHWAY

*

- o

]

Q

© 2008 ENSPM Formation Industrie - IFP Training

CEFIC document

Refining-Petrochemicals-Chemicals-Engineering

|

I F P il l f l A i N I N G

FAMILIES OF HYDROCARBONS
AND MAJOR PETROCHEMICAL DERIVATIVES

INTRODUCTION

1

I

VARIOUS MODES FOR ASSEMBLY OF CARBON ATOMS IN HYDROCARBONS

2

II -

SATURATED AND UNSATURATED HYDROCARBONS

4

III -

SATURATED CHAIN HYDROCARBONS: PARAFFINS OR ALKANES

5

1 2 -

5
6

-

IV -

V -

SATURATED HYDROCARBONS WITH RINGS: NAPHTHENES, NAPHTHENIC
HYDROCARBONS OR CYCLOALKANES

7

UNSATURATED HYDROCARBONS CONTAINING BENZENE RINGS:
AROMATICS

8

1 2 -

Benzene
Toluene

8
8

3

Aromatics in Cs: ethylbenzene, xylenes

9

-

4 5 -

VI -

n-Paraffms or straight chains alkanes
Isoparaffins or branched chains alkanes

Cumene
Polyaromatics and coke

COMPOSITION OF RAW PETROLEUM CUTS

BACHO-00038_A.A-Rev.1
© 2008 ENSPM Formation Industrie - IFP Training

10
10

12

05/06/2008

II

VII - UNSATURATED HYDROCARBONS WITH ONE OR TWO DOUBLE BONDS:
OLEFINS OR ALKENES AND DIOLEFINS OR DIENES

2
3

-

Propylene or propene
Propadiene or allene

15
16

4

-

Butenes

17

5

-

1,3-butadiene

17

VIII - UNSATURATED HYDROCARBONS WITH ONE TRIPLE BOND: ACETYLENICS OR
ALKYNES
1 2 3 -

IX -

cno-s A A

13

Acetylene
Methyl acetylene or propyne
Compounds with four carbon atoms with a triple bond

SULFUR COMPOUNDS

18
18
18
18

19

1

-

Hydrogen sulfide H2S

2

-

Mercaptans

19

3
4

-

Sulfur compounds
Ttvocyclic compounds

20
20

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

19

1

INTRODUCTION

Hydrocarbons are chemical compounds composed of only two elements: carbon and hydrogen. They are
very diverse because of the extreme ease with which the carbon atom forms bonds with other atoms. They
can be grouped into families or classes with characteristic

properties.

The olefins or alkenes and aromatics are two families of hydrocarbons that are particularly important in the
world of petrochemistry. They include a certain number of compounds such as ethylene, propylene, etc. for
the ofeffns: benzene, xylenes,
number of modern synthetic

... for the aromatics, which are the basis for the manufacturing

of a large

substances.

With the olefins and aromatics, other families of hydrocarbons are found in petrochemical plants. There are
the paraffins or alkanes, naphthenes or cycloalkanes, diolefins or dienes and acetylenics or alkynes.
The purpose of the following study is to specify the chemical composition of the various categories of
hydrocarbons and to demonstrate the particular technical and economic importance of some of them.
With the families of hydrocarbons that are composed of only carbon and hydrogen, there are also compounds
that contain other elements such as sulfur, nitrogen and oxygen. The following is limited to a presentation of
the families of hydrocarbons and sulfur-containing

compounds

however.

Before considering the various families and identifying within each of them the most important compounds for
petrochemistry,

we must understand the rules that govern the modes for assembly of atoms and especially

those for carbon atoms.
The presentation

of the various families that follows is supplemented

important petrochemical

in appendix by figures for the most

compounds that indicate the methods for obtaining them, the uses and the main

outlets.

00038_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

2

VARIOUS MODES FOR ASSEMBLY OF CARBON ATOMS IN HYDROCARBONS
The variety of hydrocarbons is due essentially to the capacity of carbon atoms to form long chains, allowing
for extremely diverse combinations. The assembly of carbon atoms in association with hydrogen atoms is
based on very precise rules however:
-

the hydrogen atom is monovalent (valency = 1). It thus forms one single bond with other
atoms. This allows it to bond with carbon in hydrocarbons with one atom of hydrogen per
bond remaining free in the carbon-carbon assemblies.

H
the carbon atom is tetravalent (valency = 4) which means that it must form four bonds with
other atoms within molecules.

The symbolic representation used is the following
when there are four single bonds with other
atoms

4 single bonds

In the case of one carbon atom bonding to four hydrogen atoms, we have the methane
molecule, the simplest hydrocarbon, with chemical formula CH4.

H

H-C-

Methane CH4

h

H
The carbon atom also has the property of being able to form a double bond to another
carbon atom.
\

c

*c

2 single bonds
1 double bond

The simplest hydrocarbon with a double bond is ethylene C2H4

C

H

00038_A_A

/

E C

EthyleneC H
2

x

H

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4

3

In some cases two carbon atoms can form a triple

C —c

bond between them.

1 double bond
1 triple bond

The hydrocarbon corresponding to two carbon atoms is

H -C

S

C

-H

acetylene C2H2.

AcetyleneC H
2

2

There is also a particular structure characteristic of aromatic hydrocarbons called the
benzene ring in which 6 carbon atoms in a hexagon are linked by the equivalent of 3 single
bonds and 3 double bonds.

For each carbon atom
2 single bonds
1 double bond

Benzene C6H6 is the first aromatic hydrocarbon

H

C-H

H-C

11

1

„C-H

H-C.
N

Benzene CqHq

C
i

H

Given the various possibilities for assembling carbon atoms, there are in nature an extremely large
number of hydrocarbons found in crude oil and natural gases. There are also those that do not exist
in nature but that the petrochemistry industry can synthesize, for example the olefins or alkenes.

00038_A_A

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4

II -

SATURATED AND UNSATURATED HYDROCARBONS
An initial factor that allows us to differentiate hydrocarbons (figure 1) is the nature of the carbon-carbon bonds
that exist within the molecules.
We thus distinguish:
-

SATURATED HYDROCARBONS, w h i c h have only single carbon-carbon bonds, the
other available positions being linked with hydrogen
In this category we find two main families:

paraffinic hydrocarbons or paraffins or alkanes in which carbon atoms form
straight or branched chains

naphthenic

hydrocarbons

or

naphthenes,

also

called

cycloparaffins

or

cycloalkanes in which the carbon atoms form rings (generally of 5 or 6 carbon
atoms)
-

UNSATURATED HYDROCARBONS, which have double or triple carbon-carbon bonds
or benzene rings. The corresponding families are the following:

olefinic hydrocarbons or olefins or alkenes have a double bond. The carbon
atoms form chains or rings

diolefinic hydrocarbons or diolefins or dienes have two double bonds

acetylenic hydrocarbons or alkynes have a triple bond

aromatic hydrocarbons have at least one benzene ring

There are also mixed hydrocarbons which can contain a double bond and a triple bond or a double bond and
a benzene ring, for example.
The distinction between saturated and unsaturated hydrocarbons is justified by the fact that unsaturation is a
deficit of hydrogen that offers the possibility of chemical combinations with unused chemical bond positions.
Unsaturated hydrocarbons, especially olefins and diolefins, have a particular chemical reactivity that is very
valuable for the petrochemistry industry in that it allows for the development of numerous compounds and
synthetic materials.

Saturated hydrocarbons

Unsaturated hydrocarbons

paraffins or alkanes
naphthenes or cycloalkanes

olefins or alkenes
diolefins or dienes
acetylenics or alkynes
aromatics

00038_A_A

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5

III -

SATURATED CHAIN HYDROCARBONS: PARAFFINS OR ALKANES
The molecules of these hydrocarbons are composed of chains of carbon atoms saturated by hydrogen.
We distinguish:
-

normal paraffins or n-paraffins (straight chain alkanes) that are composed of molecules in
which the carbon atoms form straight chains,

-

isoparaffins or branched paraffins (branched chain alkanes) in which the carbon atoms
form branched chains.

Paraffins, normal or iso, are widely found in natural gases, crude oil and oil cuts used by petrochemical units.
The structure of the carbon atom chain gives them quite different properties however.

1-

n-PARAFFINS or straight chain alkanes
Figure 2 gives the formulae and physical constants of some normal paraffins.
The first of them is methane C H 4 which is the main constituent of natural gas. The chains can be very
long, sometimes exceeding 50 carbon atoms. Crude oil thus contains a range of paraffinic
hydrocarbons from CH4 to C50H102 and more.
Taken individually, the n-paraffins are in the gaseous phase at room temperature when the chain of
carbon atoms contains 4 atoms at most (Ci to C4); they are in the liquid phase from C 5 to C16 and in
the solid phase thereafter.
The length of the carbon chains is in a direct relation with the boiling points of the hydrocarbons and it
determines their place in the various oil products as shown in figure 3.
This figure shows in particular that the most common naphthas correspond to cuts composed of C5 to
C10 hydrocarbons (boiling points between room temperature and 200°C).
We can then define a general formula for the hydrocarbons of this family, noting that a paraffin
containing n carbon atoms has 2 n + 2 hydrogen atoms, which gives the following general formula:

General formula for paraffins
C H2n+2
n

00038_A_A

© 2008 ENSPM Formation Industrie - IFP Training

6

The nomenclature for n-paraffins uses the ending | - ane |

preceded by a prefix that indicates the

number of carbon atoms of the straight chain.

Number of atoms
of carbon

1

2

3

4

5

6

7

8

9

10

Prefix

meth.

eth.

prop.

but.

pent.

hex.

hept.

oct.

non.

dec.

2-

ISOPARAFFINS or branched-chain alkanes
Branched structures appear for paraffins starting with chains of 4 carbon atoms C4H10. There are two
compounds corresponding to this formula:

BUTANE
C4H10

n-paraffin

isoparaffin

n-butane

isobutane

H H
H-C-C
I

I

H

H

H

H

H

H

i

i

H - C - C - C - H

C - C - H
I

H
'

I

H

I

H

'

H
H-C-H

tbp = -11.7°C

tbp = - 0 . 5 ° C

5

sp.gr^ = 0.573

5

s p . g r ] = 0.585

We see that the change in structure gives isoparaffins, physical properties that differ from those of nparaffin.
Isoparaffins, called by the name of the corresponding n-paraffin preceded by the prefix ISO for the
sake of simplicity, become more and more numerous as the chain of carbon atoms grows longer.
in C
ISOPARAFFINS

in C

5

2

8

18

in C o
2

366.318

isopentanes
isooctanes
iso

C20

The properties of isoparaffins remain quite close to those of the n-paraffins with regard to density and
boiling point. They differ however with respect to one essential characteristic: combustion behavior in
gasoline engines. They have an octane number much higher than that of n-paraffins.
00038_A_A

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7

IV - SATURATED HYDROCARBONS WITH RINGS:
HYDROCARBONS OR CYCLOALKANES

NAPHTHENES OR NAPHTHENIC

This is a family of hydrocarbons widely found in crude oil and natural gas condensates.
Naphthenic hydrocarbons are characterized by the presence in their molecules of saturated rings that most
often have 5 or 6 carbon atoms. The main identifying features of this family are thus hydrocarbons with 5
(cyclopentane) or 6 carbon atoms in a ring (cyclohexane).

Cyclopentane

H

s

H

r

r '

H

Cyclohexane

c A

Je>

MJR)

\ /^H
H' "H

H

i

Q

Q-

Hn

'

5

15

.

H
C H

1 0

6

tbp = 49.3° C

sp.gr

H

X

H
C H

H

i

= 0.750

t

b p

1 2

= 80.7° C

sp.gr

15

= 0.783

There are many naphthenic hydrocarbons but only cyclohexane is an important petrochemical intermediary.
It is obtained from benzene and 95 % of its production is used to synthesize Nylon-type polyamide
compounds.
Compared with paraffins, naphthenic hydrocarbons have the following properties:

OOO38_A_A

-

boiling point slightly higher with the same number of carbon atoms

-

higher density

-

greater C /H ratio (less hydrogen atoms for same number of carbon atoms). This leads to a
lower combustion heat

© 2008 ENSPM Formation Industrie - IFP Training

8

V•

UNSATURATED HYDROCARBONS CONTAINING BENZENE RINGS: AROMATICS
1-

BENZENE
The aromatics are the third large family of hydrocarbons found in crude oil. These compounds are
derived from benzene C6H6 a ring-shaped molecule composed of 6 carbon atoms apparently linked by
single and double bonds.

Benzene
C6H6

H-C

C-H

I

II
t b = 80°e
P

C

H

H

sp.gr

15

= 0.8S
X

H

o
Q

In fact the six carbon-carbon bonds are equivalent and in between single bonds and double bonds. For
this reason, the representations below are often used:

or

Benzene is an essential raw material in petrochemistry. Figure 4 shows the ways to obtain it and
its main uses. Benzene is also present in gasoline but the content is limited because of its toxicity.
The aromatic hydrocarbons have at least one benzene ring that gives them particular properties.
Derivatives are obtained by substitution of the hydrogen atoms of benzene by: methyl (- CH3),
ethyl (- C2H5) radicals, etc.

TOLUENE

In the toluene molecule, a hydrogen of benzene is
replaced by a methyl group (- CH3). As for benzene,
t

b p

= 110.6°C

sp.gr

15

= 0.871

toluene has very good solvent properties and has a
very high octane number while its toxicity, much less
than that of benzene, makes it preferable for uses in

Toluene

C7H8

gasoline and industrial solvents.

A large amount of toluene is made into benzene because of its important petrochemical uses that
were already mentioned. Figure 5 provides the main data for toluene.

00038_A_A

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9

AROMATICS IN C : ETHYLBENZENE, XYLENES
8

Ethylbenzene

CH

3

t

b p

= 136.2°C

spgr

15

= 0.871

Ethylbenzene is mostly obtained from
alkylation of benzene by ethylene
and
is
almost
entirely
dehydrogenated to make styrene.

Ethylbenzene CgH-io

Xylenes

The three xylenes or dimethyl benzenes are distinguished by the respective positions of the methyl
groups on the aromatic ring:

Ortho

Meta

CH

3

CH

3

Para

Xylenes ( C H )
8

tbp = 144.5°C
spgr

15

= 0.884

Orthoxylene

1 0

thp = 139.1°C
spgr

15

= 0.868

Metaxylene

t p = 138.4°C
D

spgr

1 5

= 0.865

Paraxylene

We see that the xylenes have very close volatilities, which makes their separation and purification
difficult. As shown in figure 6 for aromatics in Cs, only ortho and para xylene have important uses in
petrochemistry.
Orthoxylene is used to make dioctylphtalate, a plasticizer for PVC in particular.
Paraxylene is processed and used to make PET or polyethyleneterephtalate.

00038_A_A

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10

CUMENE
Cumene is obtained by alkylation of benzene with propylene. This compound is a Cg aromatic used in
making phenol and acetone.

CH3-CH -CH3
t

b p

= 152.4°C

spgr

15

= 0.866

Cumene C g H ^

POLYAROMATICS AND COKE
Aromatics with large numbers of carbon atoms generally have several attached benzene rings on
which there may be branched hydrocarbon chains. These aromatic hydrocarbons are generally called
"polyaromatics" and are derived from the following hydrocarbons:
-

naphthalene corresponding to two rings stuck together

Naphtalene C^QHS
tbp = 218°C
d

1 5

Biaromatic
hydrocarbon

= 1.010

tf,usion = 80.5°C
anthracene corresponding to three rings stuck together in a row
Anthracene

C14H10

tbp = 342°C
1

d 5 = 1.25

§

tfusion = 216°C

5

Triaromatic
hydrocarbon

And very complex compounds such as ovalene with 8 rings.

Polyaromatic
hydrocarbon

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

11

There are also compounds with very high C/H ratios, solid, very rich in carbon and remaining in the
solid phase in process conditions that are commonly referred to as "coke".
Compared with paraffinic and naphthenic hydrocarbons, aromatic hydrocarbons are characterized by:
-

a very high density in the liquid phase for volatility comparable to that of the naphthenes

-

a very high octane number for single-ring aromatics that is greatly appreciated for
gasoline engine fuels. The polyaromatics found in diesel fuel cuts are a nuisance however
(bad cetane index, tendency to clog injectors)

00038_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

12

VI -

COMPOSITION OF RAW PETROLEUM CUTS
Raw petroleum cuts, i.e. cuts directly from crude oil or natural gas condensates are mixtures of different
hydrocarbons from different families.
The overall properties of these cuts thus depend on the respective proportions of the families. They may be
more paraffinic, naphthenic or aromatic depending on the nature of the cut and the origin of the crude or
gases.
Laboratories seek to determine the P.O.N.A. of a cut, i.e., the respective proportions of paraffins (P), olefins
(0), naphthenes (N) and aromatics (A) present in the cut analyzed. We thus use the term "P.I.A.N.O."
(paraffins, isoparaffins, aromatics, naphthenes, olefins).
As an example, the table below gives the composition of some naphthas.

% Volume
Crude
Kirkuk

Hassi
Messaoud

Cut (fC) _

0

.%

d

1 5

| ji><i\ C 5 —132

0.696

"C.C5-173

0.722

C -132

0.703

C5-173

0.725

5

P

N

A

77.1
69.8

20.5
22.4

2.4

72.6
65.7

22.8
26.1

4.6
8.2

7.8

This type of analysis is very interesting for determining the optimum processing conditions for a feedstock in a
steam cracker.

00038_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

13

VII - UNSATURATED HYDROCARBONS WITH ONE OR TWO DOUBLE BONDS: OLEFINS
OR ALKENES AND DIOLEFINS OR DIENES
Olefins or alkenes are hydrocarbons in chains or rings in which we find one carbon-carbon double bond. A
compound may have two double bonds, we then speak of a diolefin or diene. Due to the presence of the
double bonds, olefins and diolefins belong to the family of unsaturated hydrocarbons in which they form a
group of considerable value. This unsaturation gives them high chemical reactivity, which explains why they
are absent from natural hydrocarbon deposits. These compounds had plenty of time to react to produce stable
hydrocarbons.
It is therefore necessary to make them in so-called cracking units, whence the existence of petrochemical
complexes using steam crackers. Among other products, they produce the major petrochemical
intermediaries: ethylene, propylene, isobutene and the butenes for various specialized branches of the
chemical industry.

ETHYLENE
Ethylene or ethene is the most structurally simple olefin and the most important one from an economic
standpoint.

h \\
H

,

, H'

/ '
C

=

C

,

Ethylene

C2H4

V-104-C

H

I

At room temperature it is a gaseous compound that must be brought to low temperatures to achieve
the liquid phase.
Ethylene is mostly obtained by steam cracking of ethane, naphtha or heavier cuts.

H

H

H

H

H

H

1
1

1
1

1
1

1
1

1
1

1
1

C-- C - - C - - C - - C - -C

-IE

Thanks to the reactivity of the double bond, the ethylene molecule can be added to itself many times.
We then speak of a polymerization reaction, yielding long molecules called macromolecules.

1

H

H

H

1
1

1
1

1
1

c - C - - C - C

1
1

1
1

1
1

1
1

1
1

1
1

1
1

1
1

1
1

1
1

H

H

H

H

H

H

H

H

H

H

Polyethylene
-(CH -CH )
2

2

n

The diagram above shows a polyethylene molecule resulting from addition of a very large number of
ethylene molecules. We say that ethylene is the base molecule, called a monomer, of a
macromolecule called a polymer.
Polymeric chains have variable properties as a function of the polymerization conditions.

00038_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

I

14

figure

As indicated in

7, ethylene is used to manufacture several important monomers and

petrochemical intermediaries such as:
• Vinyl chloride

H

CI

\

CH2 = CHCI

/

Vinyl chloride

C= C
/

C H CI
2

\

t

H

b p

-

3

= -13.4°C

§

H

I

which, by polymerization yields polyvinyl chloride (PVC)
• Styrene

CH = CH2

C = C
1 1

Styrene
C H
8

t

8

= 145.2°C

b p

from which many qualities of polystyrene are made.
• Ethylene oxide

H

H

\

CH2 X

CH2
/

Ethylene oxide

c - C

H

0

/

/

X

/

X

0

C H 0
2

H

4

*bp = 10-5-c

used to make monoethylene-glycol for anti-freeze.

^ \

CH20H -

CH20H

/ ^

Ethylene glycol

C- C
W

/

\

l

C H 0
2

X

H

6

2

t =198.9°C
b p

OH OH
Acetaldehyde

H
CH3-CHO

H - C - C
I

H

H

Acetaldehyde

7

CH0
2

^ 0

l

b

P

=

4

2 0

which is an important intermediary in making acetic acid and acetate derivatives.

00038_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

8

- °

c

15

• Vinyl acetate

H

CH3 - COO - CH = CH2

0 - CH = C H 2

Vinyl acetate
C 4 H 6

H-C-c'
|

V )

°

_

2

1
c

tbp = 72.2°C

H
which is used for manufacturing resins and glues.

Ethanol

CH3CH2OH

H

H

I

|

Ethanol

H-C-C-OH
I

I

|_|

|_j

c H 0
2

1

6

m
t

b p

= 78,3°C

£

Used as a solvent, it is also used for production of acetaldehyde.

2-

PROPYLENE OR PROPENE
Propylene is the only C3 olefin. It is associated with ethylene in steam cracking effluents but it is also
obtained, in refineries, from units for catalytic cracking of heavy cuts. New processes are used to
obtain it by dehydrogenation of propane.
Propylene has physical properties close to those of propane:
Y\

CH = CH-CH3
2

X

|-|

Propylene

C = C - C - H
H

S

t

spgr

15

= 0.520

2

It is gaseous at room temperature but can be stored in the liquid phase under pressure.
Polymerization of propylene yields polypropylene.
Propylene is also used in the synthesis of many compounds (figure 8), the most important of which
are:

Acrylonitrile

H

CH2 = CH -

C = N

H

c = C

7

the basis for the manufacturing of acrylic fibers.

00038A.A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

Acrylonitrile
C

3H N
6

0

1

16

• Propylene oxide

H ^

CH2-CH-CH3

H

H

|

|

Propylene oxide

C - C - C - H

0

O

c H 0
3

6

T B P = 6 3

H

°

C

used after transformation in polyurethanne foams.

Cumene

CH3-CH-CH3

I
H-C'^

^ C - H

I

Cumene
C

II

H - n

C-H

t

b p

H

9 12

= 152.4°C

c
s

H

Cumene was already presented as the raw material for production of phenol and acetone.
• Heavy alcohols
Propylene is used to make heavy alcohols, i.e. compounds containing the alcohol group branched on a long carbon chain.

3-

PROPADIENE OR ALLENE
Propadiene is the three carbon atom diolefin found in the C3 cut of steam cracking effluents.

CH = C = CH
2

2

~

c

It is one of the impurities that must be eliminated from this cut.

00038_A_A

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I

OH

17

4-

BUTENES

\

We distinguish several butenes of formula C 4 H 8 :

H

C 3

CH2 = CH - CH2 - C H

3

CH

CH2 = C - C H

X

3

x

1

"

1 butene
t

b p

Isobutene

= -6.3°C

spgr

15

t

= 0.601

spgr

15

t

= 0,601

b p

S

H

spgr

C H Q

H

3

2,trans-butene

= 3.7°C
15

= C

1

2,cis-butene

= -6,9°C

b p

H

3

\
1

H

^ L - M

CH

3

c'

C =

3

CH

t

= 0.627

b p

spgr

= 0.8°C
15

j

= 0.610

Among these compounds, isobutene has the greatest industrial importance.
Isobutene is used in the making of MTBE (Methyl tertiobutylether), polyisobutene and butyl rubber
(figure 9).
The remaining butenes are used in various ways depending on the site.

5-

1,3-BUTADIENE
1,3-butadiene is a C4 diolefin:

H \

/ H

C = C~ C
H

/

i

I

H

H

=

C

1,3-Butadiene
tu„ = 4 4°n
b p

\H

The presence of two double bonds in the molecule leads, during polymerizations involving 1,3butadiene, to the residual presence of an unused double bond within the polymers. This characteristic
allows us to then use the reactivity of this double bond for various branchings. The polymers obtained
are rubbers whose mechanical properties can be modified by making bridges between the polymer
chains, usually with sulfur. The mechanism is used in the vulcanization operation that produces
industrial rubber of homogeneous quality and with the resistance needed for various uses.

SULFUR

Free

I
^

double

s

n

I
S

m

I
Sp

bonds
ED
to

Before vulcanization

1,3-butadiene is used in making many polymers

00038_A_A

After vulcanization there are sulfur bridges

g

between the carbon chains

o

(figure 10).

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

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18

VIII - UNSATURATED HYDROCARBONS CONTAINING A TRIPLE BOND: ACETYLENICS OR
ALKYNES
Acetylenics are hydrocarbons in which there is a carbon-carbon triple bond which gives this family of
hydrocarbons very high chemical reactivity. When they are pure they tend to decompose spontaneously and
violently.

1-

ACETYLENE
Acetylene is the simplest triple bond hydrocarbon.

H-C = C - H

Acetylene

£

t =-84°c

I

b

Acetylene was widely used in the past as a synthesis reagent. Its importance has considerably
decreased but it still has some specific uses.
In steam cracking, acetylene is present in small quantities in the C

2

cut with ethylene and ethane and

is an impurity to be eliminated.

2-

METHYL ACETYLENE OR PROPYNE
Methyl acetylene is the triple bond compound with three carbon atoms.
Methylacetylene

CH3 — C =

CH

t

b

:

23i

2°c

P

It is present in the C3 steam cracking cut.

COMPOUNDS WITH FOUR CARBON ATOMS WITH A TRIPLE BOND
Ethylacetylene (butyne) and vinyl acetylene (1-butene, 3-yne) are both present in the C4 steam
cracking cut.

C H — CH2 — C = CH

E

~ "

3

CH2 = CH - C = CH

00038_A_A

©2008 ENSPM

e

Vinyl acetylene
t

b p

=

5.rc

Formation Industrie - IFP Training

19

IX-

SULFUR COMPOUNDS
Sulfur is a divalent element [ - S - | associated with hydrogen and carbon in 4 types of principal compound
(Figure 7):
-

1-

hydrogen sulfide
mercaptans
sulfides
thiocyclic compounds (containing sulfur in a ring)

HYDROGEN SULFIDE
Hydrogen sulfide ( H S ) is not found in petroleum products but it does exist in small amounts in crude
2

oils and in varying amounts in natural gas: 0.3% volume in gas from the Zakum field (Abu Dhabi), and
15% volume in gas from Lacq (France). It is also present in large quantities in the refinery as many
units generate H S as a compulsory step in the desulfurization process.
2

Hydrogene

sulfide

H-S-HorH2S
t

b p

= -60°C

Refineries therefore have to handle and process large quantities of H2S and have to apply extremely
strict safety regulations as it is a very toxic and dangerous gas. It is also corrosive, particularly at
low temperatures when dissolved in water where it breaks down into sulfhydride acid.

2-

MERCAPTANS
Mercaptans are composed of the functional combination

| — S — H | associated with a hydrocarbon

chain represented by the letter R.

General formula
Mercaptans

R - S - H

Mercaptans occur in most petroleum cuts and they have the following drawbacks:
-

they are acid
they have an obnoxious smell

Refinery installations therefore generally have to include equipment for removing these compounds.

00038_A_A

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20

SULFIDES
In these compounds the sulfur atoms are linked to two hydrocarbon chains. The sulfur therefore forms
an intermediary between the two chains and a distinction is made between:
-

sulfides in which there is only one sulfur atom:

R - S - R '
-

disulfides in which there are two sulfur atoms:

R - S - S - R '
-

polysulfides in which there are several sulfur atoms:

R - S - S

...S-R'

These compounds occur in crude oils and petroleum products. Unlike mercaptans, they have the
advantage of not being acid which means they are not corrosive and their low volatility greatly
reduces their smell.

THIOCYCLIC COMPOUNDS (containing a sulfur atom in a ring)
This group of sulfur compounds is the most commonly found in crude oils and petroleum products and
is chiefly derived from thiophene:

Thiophene

c

- c

II
c

H

y

C4H4S

II
t b

C
N

g'

X

H

P

= 8 4

°

c

sp.grJ5 = 1.070

and from benzothiophene

H
C
^

H-C^
1
C
H

H
x

/

0%/

C - C
11

11

C

C
V

s

Benzothiophene
CsH S
6

tbp = 220°C
N

H

sp.gr15= 1.165

H
Their characteristics are similar to those of aromatic hydrocarbons: unsaturated rings and good thermal
stability. They are neutral and non-corrosive.
The desulfurization of petroleum products consists in destroying these compounds, which is not an
easy task, particularly in the case of very heavy thiophenic compounds.

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

e n s p m
If-P • 7 R A I N I N G

FAMILIES OF HYDROCARBONS
AND MAJOR P E T R O C H E M I C A L DERIVATIVES

DIFFERENT TYPES OF HYDROCARBONS

Figure 1

Hydrocarbons: N-PARAFFINS

Figure 2

COMPOSITION AND BOILING INTERVALS OF HYDROCARBONS PRESENT
IN THE MAIN PETROLEUM PRODUCTS

Figure 3

BENZENE: Origin - Production - End uses

Figure 4

TOLUENE: Origin - Production - End uses

Figure 5

Cg AROMATICS: Origin - Production - End uses

Figure 6

ETHYLENE: Origin - Production - End uses

Figure 7

PROPYLENE: Origin - Production - End uses

Figure 8

ISOBUTENE: Origin - Production - End uses

Figure 9

1,3-BUTADIENE: Origin - Production - End uses

Figure 10

MAIN PROPERTIES OF TYPICAL SULFUR COMPOUNDS

Figure 11

MAIN PRODUCTION PROCESSES OF OLEFINIC AND AROMATIC INTERMEDIARIES ...Figure 12
OLEFINS AND AROMATICS PRODUCTION

^ BA CHO - 00039. A A - Rev. 2

CO) 2008

ENSPM Formation Industrie - IFP Training

Figure 13

05/06/2008

I

enspm
FORMATION INDUSTRIE
IFP

TRAINING

DIFFERENT TYPES OF HYDROCARBONS

SATURATED HYDROCARBONS

UNSATURED HYDROCARBONS

with single bonds

Carbon atoms in

• Chain structure •

PARAFFINS

— Figure 1 —

with double bonds

with triple bonds

Molecules with

Hydrocarbons with

Carbon atoms in

Carbon atoms in

— Cycles —

- Benzenic cycles -

— Chain structure •

— Chain structure -

NAPHTENES

AROMATICS

1 double bond

1 triple bond

OLEFINS

ACETYLENICS
4

Straight chain

Branched chain

N-PARAFFINS

ISOPARAFFINS

2 double bonds

DIOLEFINS

CYCLOPARAFFINS

— Examples

Olefin

Diolefin

EXISTING HYDROCARBONS IN CRUDE OIL

4r

© 2008 ENSPM Formation Industrie - IFP Training

UNSTABLE OR VERY UNSTABLE HYDROCARBONS

Hydrocarbons
e n s p m

— N-PARAFFINS —

FORMATION INDUSTRIE
IFP

— Figure 2 —

TRAINING

Number
of carbons

Methane

c

1

Ethane

c

2

Propane

c

3

Butane

c

4

Pentane

c

5

Hexane

c

6

Heptane

Octane

Nonane

••

Hexadecane
••


Eicosane




Triacontane


— Straight chain alcanes —

CH,

bp = -161.5°C

C H
2

bp = - 89°C

6

CoH
3 8

C H
4

C H
5

6

7

8

4

.15
sp.gr " = 0.631
4

1

bp = + 69°C

1 4

C H

c

.15
s p . g r =0.585

bp = + 36°C

1 2

C H

7

4

bp = -0.5°C

1 0

1 6

G A S

.15
sp.gr' =0.505

bp = -42°C

n

c

5

sp.gr = 0.664
4

bp = + 98°C

sp.gr

1 5

bp = + 126°C

4

L I Q U I D

= 0.688

sp.gr

bp = + 151°C

4

=0.707

sp.gr

, J

= 0.722
bp = 287°C

c

16

C

H

16 34

mp = + 18°C
bp = + 344°C

c

c

Physical state
at 15°C - 1 ATM

20

C

H

20 42

mp = +36°C
bp = + 450°C

30

C

© 2008 ENSPM Formation Industrie - IFP Training

H

30 62

mp = +66°C

e n s p m
COMPOSITION AND BOILING INTERVALS

FORMATION INDUSTRIE
n

TRAINING

OF HYDROCARBONS PRESENT
IN THE MAIN PETROLEUM PRODUCTS

200
o

ol

LNG

'

C1

i
+
CO

-100

<
L.P.G.
CARBURANT

C2

COMMERCIAL!
PROPANE

C3

COMMERCIAL
BUTANE

C

CO
LU

LU
> LU

PETROCHEMICAL

O

CO
<

NAPHTHAS

O

_i

s
o

o
<2

hZD
<

/DIESEL

LU
Q
LU

s

a:

JETA1
FUEL

AND

O
ZD

\

3>f

C5
C6
+ 100

3

t?

C8

O

-Cn

+ 200

C14
.ft"'

HOME-

o
o

<

4

+ 300

HEATING

LU 0£
I— OL

FUEL

+ 400
CO
II Q

IFP

<

O

LU
CO

+ 500

<t o
LU
00
CO
LU
X

ZD

1

Range of
products

+ 600

Boiling point
and number of carbon atoms
in hydrocarbons
© 2008 ENSPM Formation Industrie - IFP Training

Hi,

e n s p m
B E N Z E N E : Origin - Production • End uses

FORMATION INDUSTRIE
IFP

a

TRAINING

End uses
PRODUCTION CAPACITIES

39 Mt/y

— Figure 4 •

MAIN END USES FOR BENZENE

% WORLD
Production of styrene

World

STYRENE
PRODUCTION
29.7 Mt/y

50%

co

World

6.9 Mt/y

Western Europe

0.9 Mt/y

France

Benzene

Ethylene

C6Hg

C2H4

Ethylbenzene
C H
8

Styrene

Hydrogen

C H

H

8

1 0

8

2

MAIN PRODUCTION UNITS

Production of phenol and acetone
Al

PHENOL-ACETONE

20%
Benzene
C H
6

6

Propylene

Cumene

C3H6

C9H12

Oxygen
0

Production of cyclohexane
Toluene dealkylation
•Transalkylation

4

CYCLOHEXANE
20%

15%

00

[

I

+

HYDROGENATION

00

>

Benzene
C H
6

6

Hydrogen
3H

2

© 2008 ENSPM Formation Industrie - IFP Training

Cyclohexane
C H12
6

2

Phenol

Acetone

C H OH

CH3CO C H

6

5

3

enspm
FORMATION INDUSTRIE
IFP

TOLUENE: Origin - Production - End uses

TRAINING

End uses

• Figure 5 —

MAIN END USES FOR TOLUENE

% WORLD
PRODUCTION CAPACITIES
Production of benzene
21 Mt/y

World

PRODUCTION
14 Mt/y

World

1.9 Mt/y

Western Europe

60 kt/y

HYDRODEALKYLATION

BENZENE

40%

France

MAIN PRODUCTION UNITS

Toluene

Hydrogene

Benzene

Methane

C H

H

C H

CH

7

8

2

6

6

Benzene and xylene production

BENZENE-XYLENES

DISPRQPQRTIQNATI

16%
77%
Toluene
V

Toluene

J

w

Y

2C H
7

8

ii:«|ui[:)i|.
© 2008 ENSPM Formation Industrie - IFP Training

Xylenes
Benzene
C H
6

6

(ortho. meta. para)
CsHlO .

4

enspm
C s AROMATICS : Origin - Production - End uses

FORMATION INDUSTRIE
IFP

• Figure 6 -

TRAINING

PRODUCTION CAPACITIES
3
12

Mt/y
Mt/y

End uses

OX World
dePX

% WORLD

MAIN END USES

ETHYLBENZENE
Production of styrene

PRODUCTION

DEHYDROGENATION
2.2
9
20

Mt/y
Mt/y
Mt/y

OX
PX
EBz

STYRENE

99%

MAIN PRODUCTION UNITS

Ethylbenzene

Styrene

Hydrogen

CsH-io

C H

H

8

8

2

• XYLENES
Production of phtalic anhydride from ortho-xylene

NIDATION
CO
Orthoxylene
C H
8

1 0

Oxygen
30

Phtalic anhydride
C H 0

2

8

Water
3H 0
2

4

3

Production of terephtalic acid (T.P.A) and dimethylterephtalate (DMT) from paraxylene
:|t:il'iiu
!:Me!'!iin*a

85%
-—'

S

OXIDATION

. £ C>Paraxylene
f
Others

C

C

H

8 10

6%

Oxygen
3 0

Terephtalic acid
C H 0

£(;-

2

4 o

8

6

a

OXIDATION

i

C Hio
8

Methanol
2 CH OH
3

© 2008 ENSPM Formation Industrie - IFP Training

2

4

<Oj

ESTERIFICATION
Paraxylene

Water
2H 0

Dimethylterephtalate
C

H

10 10°4

Water
4H 0
2

enspm
FORMATION INOUSTRIE
IFP

ETHYLENE: Origin - Production - End uses

TRAINING

Figure 7 •

END USES
CAPACITIES OF PRODUCTION

MAIN END USES FOR ETHYLENE

% WORLD

Production of polyethylenes (LDPE, HDPE, LLDPE)
100.9 Mt/y

World

POLYETHYLENES
PRODUCTION
90 Mt/y
18.75 Mt/y

Q ^ ^ P +

+

Qm~m&

)LYMERlZATION

<

i & A i

i\i\j\<

World

n times

Western Europe

Polyethylene
(C H )n

Ethylene

2

3 Mt/y

mar)

56%

Domestic

C H
2

4

4

Production of vinyl chloride

MAIN PRODUCTION UNITS

SEVERAL
STEPS

VINYL
CHLORIDE

0

15%
Ethylene
C H
2

4

Chlorine
Cl
2

Vinyl chloride
C H CI
2

3

Hydrogen chloride
HCI

Production of ethylene oxide

ETHYLENE OXIDE

r

12%
Ethylene
2C H
2

4

Oxygene
0
2

STYRENE

7%

Production in two steps (see on figure 4 • BENZENE)

© 2008 ENSPM Formation Industrie - IFP Training

Ethylene oxide
2 C H 0
2

4

o

-

P R O P Y L E N E : Origin - Production • End uses

enspm

— Figure 8 —

FORMATION INDUSTRIE
IFP

TRAINING

END USES

MAIN END USES FOR PROPYLENE

% WORLD
Production of polypropylene

CAPACITIES OF PRODUCTION

POLYPROPYLENE
56.7

Mt/y

World

e * ^

c * ^

+

_ra1YMERIZATION

50%

Q Q Q Q. Q Q
v

v

Polypropylene

Propylene n times C3H6

(C H )n
3

ACRYLONITRILE
47.2

Mt/y

13.5

Mt/y

Western Europe

2.5

Mt/y

Domestic

6

Production of acrylonitrile

PRODUCTION

12%

AMMOXIDATION
Propylene
2C H
3

6

Ammonia
2 NH
3

Acrylonitrile
2C H N

Oxygen
3 O2

3

3

Water
6H 0
2

Production of heavy alcohols

MAIN PRODUCTION UNITS

OXO ALCOHOL

9%

Propylene
6 C H6
3

Carbon
monoxide
2 CO

Heavy alcohol
C20H41OH

Hydrogen
4H
2

Water
H 0
2

Production of propylene oxide

PROPYLENE
OXIDE
+

9%
Isobutane
C4H10

Catalytic
cracking

Propylene
C H
3

6

i. >.
Oxygen
0

2

Propylene oxide
C H 0
3

6

PHENOL-ACETONE
i ' : ai' j l s * a;:

7%

>:\i

Metathesis

Production in several steps of phenol and acetone (see on figure 4 - BENZENE)

00
© 2008 ENSPM Formation Industrie - IFP Training

Tertiobutylic alcohol
C4H9OH

FORMATION INDUSTRIE
IFP

TRAINING

I S O B U T E N E : Origin - Production - End uses

— Figure 9 —

END USES
Main production units

MAIN END USES OF ISOBUTENE

% WORLD
Production of MTBE

• Steamcracking
- Catalytic cracking
- Dehydrogenation of isobutane

MTBE

ETHERIFICATSON

Isobutene

Methanol

Methyltertiobutylether

C H

CH3OH

C4H9 OCH3

4

8

Production of polyisobutene

POLYMERIZATION

POLYISOBUTENE

f

T

v

Y
Isobutene n times
C H
4

W

8

Polyisobutene
(C H )
4

Production of butyl rybber by polymerisation with isoprene as comonomer

BUTYL RUBBER %

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

8

n

enspm
FORMATION INDUSTRIE
IFP

TRAINING

— Figure 10 —

1-3 BUTADIENE: Origin - Production - End uses

END USES

MAIN USES OF 1-3 BUTADIENE

% WORLD
CAPACITIES OF PRODUCTION

Production of SBR (Styrene - butadiene rubber)
9

Mt/y

2.28 Mt/y

World
Western europe

PRODUCTION
1.97 Mt/y

>' ° *

STYRENE BUTADIENE

Western europe

'OLYMERIZATION

RUBBER 27%

Styrene
C H

MAIN PRODUCTION UNITS

8

SBR

1,3-Butadiene
C H
4

8

6

Production of polybutadiene
3

QLYMERIZATI0N

BUTADIENE RUBBER |

27%
Butadiene rubber
1,3-Butadiene n times
C H
4

6

LATEX
1

/Dehydrogenation o f ~ \
\ n butane & butene . ., /

17%

20%
© 2008 ENSPM Formation Industrie - IFP Training

(C H )n
4

6

enspm
MAIN P R O P E R T I E S OF TYPICAL

FORMATION INDUSTRIE
IFP

•Figure 11 —

TRAINING

SULFUR COMPOUNDS
HS

HYDROGEN SULFIDE

H - S

—,

2

bp = - 60°C

o

- H

gaseous at atmospheric pressure
corrosive
very toxic
MERCAPTANS

CHgSH

• Examples

1
Methyl mercaptan

H

bp = + 6°C

|3

- H

h - C - S
i

H
H

C2H5SH

H

Ethyl mercaptan

H - C - C - S - H
i

i

H

H

bp = 35°C
acid products
disagreable odour

SULFIDES, DISULFIDES

H-C - S

" C

•Examples —

C2HgS

H

C H S

H

2

6

2

S - C - h

h - C - S

bp = 37°C

Dimethyl sulfide

-H

l

i

H

H

Dimethyl disulfide

4 <

bp = 109.6°C

1

non acid products
usually no disagreable odour
unstable at high temperatures; discompose into mercaptides
— Examples —

C4H4S

THIOPHENIC COMPOUNDS

Thiophene
c

- c

II

bp = 84°C

II

CgHgS
Benzothiophene

H-C
I

c

II

-

c

II

bp = 220°C
H

H
I

H

• non acid products
© 2008 ENSPM Formation Industrie - IFP Training

enspm
FORMATION INDUSTRIE
IFP

B TRAINING

MAIN PRODUCTION P R O C E S S E S O F

Figure 12 •

O L E F I N I C AND AROMATIC I N T E R M E D I A R I E S

C cut
2

•(

Ethylene

•(

Propylene

'#11 i.f
C cut
3

C4 cut
- • ( ^ B u t a d i e n e J , ( I s o b i r t e n e J , Butenes
Gasoline

-•
•>(

Automotive fuel pool
Benzene ) , Toluene, Xylenes

•(^Benzene") , C

^

ir-Ui

fair

Ktnv/tsfifliiif

Toluene^)

j
•(^Orthoxylene) , (^Paraxylene^)
Reformate
(Gasoline)
Metaxylene

Automotive fuel pool

C cut
3

• > / Propylene )
C4 cut
•>-(
F.C.C.gasoline

Butenes
Automotive fuel pool

© 2008 ENSPM Formation Industrie - IFP Training

FORMATION INDUSTRIE
IFP

TRAINING

OLEFINS AND AROMATICS PRODUCTION

•Figure 13 —

PRODUCTS

FEEDS
PROCESSES

Propylene
World 47,2 Mt

Butene 1

CATALYTIC CRACKING

Isobutene

Ethylene
World 90 Mt

Distillates C20 to C50

Butadiene
World 9 Mt

• Ethane (C2)
. LPG (C3 - C4)

STEAMCRACKING

Benzene
World 29.7 M

• Naphtha (C5 - C10)

Toluene
World 14 Mt

CATALYTIC REFORMING
Xylenes

Heavy naphtha C7 to C10

World 11.2 Mt

© 2008 ENSPM Formation Industrie - IFP Training

e n s p m
I F P «

Refining-Peirochemicals-Chemicals-Engineering

T R A I N I N G

STEAMCRACKING

I

-

II -

III -

PRINCIPLE OF STEAMCRACKING

1

1 -

Cracking conditions

1

2
3

Yields obtained - Steamcracking feedstocks
Investments - Economic aspects

2
5

-

STEAMCRACKING UNIT

6

1 2 -

Hot zone
Compression zone

6
19

3

Cold zone

22

-

SELECTIVE HYDROGENATIONS

26

1 -

Common characteristics of hydrogenations

26

2

-

Selective hydrogenation of C

steamcracking cut

28

3

-

Selective hydrogenation of C3 steamcracking cut

30

4

-

Selective hydrogenation of C4 steamcracking cut

31

5

-

Hydrostabilization of steamcracking gasolines

31

2

05/06/2008

I

1

The first facilities for Steamcracking
main process for producing
intermediaries.

appeared in about 1920 in the United States, and it quickly became the

ethylene,

propylene,

butadiene

and other first generation

petrochemical

The main steps in the development of the process were the following:

around 1920

Fabrication of ethylene by cracking of ethane from natural gas (Union Carbide and
Carbon Co)

1942

First diesel fuel steamcracking
6000 t/year of ethylene

1950

Construction of units with capacity of up to 500001 of ethylene

1950-1960

Appearance of facilities
petrochemical naphtha.

Today, new units have production
means 1000000 t/year.

I-

normally

unit (British

producing

Celanese)

300,000

- Capacity

of

t/year of ethylene

about

from

capacities on the order of 600000 to 700000 t/year, or even more that

PRINCIPLE OF STEAMCRACKING
1-

CRACKING CONDITIONS
The cracking process involves breaking carbon-carbon or carbon-hydrogen chemical bonds within
hydrocarbon molecules. This creates other molecules, some of which, unsaturated like ethylene or
propylene, are the ones we are seeking. Cracking reactions require high input of heat energy and high
temperatures. They begin as of 400°C to 500°C, but in these conditions they do not produce the
desired products.
Steamcracking requires

-

particularly extreme conditions:

cracking temperature: on the order of 800 to
cracking residence time: 0.1 to 0.5 second

850°C

-

low pressure slightly higher than atmospheric pressure

-

dilution of the feed with large quantities of steam:

on the order of 0.6 ton per ton of

naphtha feed
These extreme conditions are reached in very special furnaces called pyrolysis furnaces. They are
justified by the analysis of figure n°1 that shows the relative stabilities of hydrocarbons as a function
of temperature. We see that the unsaturated hydrocarbons become stable with respect to saturated

hydrocarbons at

high temperatures. Ethylene for example becomes stable with respect to ethane as

of800°C.

Figure n°1

also shows that aromatic hydrocarbons: benzene, naphthalene, etc. represent a state of
natural stability and that in fact the most stable products obtained in the cracking process are

polyaromatic coke and gaseous hydrogen.
When we want to crack naphtha for example it is important to run at a very high temperature to
promote ethylene formation, but we must also limit the time of the chemical cracking reactions in order
to reduce the formation of heavy aromatic products and coke.

00040_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

2

That is why the residence time is limited to several tenths of a second by a very quick pass through a
pyrolysis furnace, with very rapid cooling or quenching of the cracked products as soon as they leave
the furnace. The most modern furnaces, called "millisecond furnaces," use residence times of less than
th

1/10 of a second compensated for by higher temperatures to increase the yield of ethylene.
The low pressure and steam act as diluents to prevent the hydrocarbon species from combining
among themselves to form hydrocarbons and coke.
The chemical reactions involved in steamcracking are extremely complex. They include primary
cracking of molecules of the feed and then secondary cracking of the cracked species obtained.
Figure n°2 shows the standard reaction diagram corresponding to a molecule of heptane (nCj) that
we find in naphthas. Cracking reactions for carbon-carbon bonds lead to hydrocarbons with shorter
chains. Dehydrogenation reactions correspond to losses of hydrogen and the yield of unsaturated
species. Addition reactions involving olefins, aromatics and especially diolefins lead to the formation
of aromatics and coke.

2-

YIELDS OBTAINED - STEAMCRACKING FEEDSTOCKS
a - Standard yields for naphtha
The diagram below shows the range of standard yields obtained from cracking of naphtha.

%
H Y D R O G E N

weight

METHANE

10
20
ETHYLENE
NAPHTHA

30

y

C CUT
2

40
ETHANE
50
60

PROPYLENE

C CUT
3

PROPANE + PROPYNE-PROPADIENE

70

1,3-BUTADIENE
OTHERS C

C
4

PYROLYSIS
90
100

0004QAA

GASOLINE
FUEL

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

4

CUT

3

We obtain a panoply of products ranging from hydrogen and methane to highly aromatic fuel oil:
-

hydrogen can, after separation, be used in facilities for selective hydrogenation of
cracked effluents (C2 cut, C3 cut, C4 cut, gasoline cut)

-

methane is an excellent fuel for steamcracking furnaces

-

the C2 cut is the largest effluent and contains mostly ethylene (about 80%)

-

the C 3 cut is very rich in propylene (about 90%)

-

the C4 cut is about half 1,3-butadiene. It also contains significant amounts of isobutene
and 1-butene

-

the gasoline cut (C5 to C10) is very rich in aromatic hydrocarbons and diolefins. The C6
part of this gasoline is rich in benzene that can be separated

-

the highly aromatic fuel oil is a heavy product of mediocre quality as a fuel but may be
desirable for its lower sulfur content

This yield grid also indicates that close to 80% of the mass of reactor effluent is composed of gaseous
compounds in normal conditions (H2, C i , C2, C3, C4).
b - Typical yields depending on the feedstock
Depending on the nature of the feedstocks, the yields can be very different. The table below gives
the standard yields obtained from steamcracking of ethane, LPG, naphtha, diesel fuel and vacuum
distillate.

FEEDSTOCKS

Ethane

Propane

Butane

Naphtha

Diesel fuel

Vacuum
distillate

Yields in % mass

PRODUCTS
Hydrogen
Methane

.

Ethylene
Propylene
Butadiene
Other C
4

Gasoline C5-2OO
Fuel oil

8.8
6.3

2.3
17.5

1.6
22.0

1.5
17.2

0.9
11.2

0.8
8.8

77.8

42.0

40.0

33.6

26.0

20.5

2.8
1.9
0.7
1.7

26.8
3.0
1.3
6.6

17.3
3.5
6.8
7.3

15.6
4.2
4.5

16.1
4.5
4.8

14.0
5.3
6.3

18.7

18.4

19.3

0.5

1.5

4.7

18.1

25.0

Ethane, the production of which is associated with that of natural gas, is a feedstock that gives very
high yields of ethylene. The corresponding yields of propylene, C4 hydrocarbons or aromatic gasolines
are very low however.
Liquefied propane and butane petroleum gas can be an alternative to naphtha for existing units.
Naphthas are the main feedstocks for steamcrackers in Europe and Japan. They supply a large range
of products: 25 to 35% ethylene, about 15% propylene, 20 to 25 % gasoline.
The heavy feedstocks: diesel fuels, distillates produce less ethylene and more fuel oil compared with
naphthas but they are often of value because they are less expensive.

00040_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

4

c - World breakdown of feedstocks
The table below shows the estimated breakdown of steamcracking feedstocks in the world for 2000
(in % weight):

Nature of feedstocks

Western

North America

Japan

World

Europe
Light hydrocarbons
Ethane-LPG

16

75

3

42

Naphthas

74

18

97

52

Diesel fuel-distillates

10

7

-

6

100

100

100

100

The diagram below gives a worldwide breakdown of the raw materials used for the ethylene
production.

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3-

INVESTMENTS - ECONOMIC ASPECTS
Steamcrackers are complex facilities requiring high investments.
The table below gives the corresponding orders of magnitude for various feedstocks based on an
ethylene production capacity of 500000 t/year (Conditions for Europe, end of 2000).

Feedstock

Ethane

Naphtha

Atmospheric diesel
fuel

Minimum investment
(millions of Euros)

330-400

460-550

560-640

Pyrolysis furnaces account for only 30 to 40% of investments. The remaining 60 to 70% is for
separation and purification facilities for commercial products.
Fuel consumption is also high. It absorbs most of the residual gas production (hydrogen + methane) in
the case of naphtha steamcrackers.

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II •

STEAMCRACKING UNIT
Steamcrackers are complex industrial facilities for which the techniques used and the operating conditions
vary greatly. They can however be divided into three main zones, each of which has several types of
equipment with very specific functions. We generally distinguish:
-

-

the hot zone including: pyrolysis or cracking furnaces, quench exchanger and quench ring,
the columns of the hot separation train
the compression zone including: a cracked gas compressor, purification and separation
columns, dryers

-

the cold zone including: the cold box, methanator, fractionating columns of the cold
separation train, the C2 and C3 converters, the gasoline hydrostabilization reactor

1-

HOT ZONE
The typical design of the hot zone of a unit processing naphtha or diesel fuel is shown in Figure n°3.
Starting from the storage area where the naphtha feed is available at room temperature, we
successively proceed with:
-

the pressurization of the feed with a pump, then preheating it by heat recovery on the
effluents of the unit in several heat exchangers

-

the breakdown of the feed in various furnaces within which thermal cracking reactions
occur in the presence of dilution steam injected into the hydrocarbon flow, the quantity of
which is a function of the nature of the feed processed

-

the brutal quenching of the furnace effluents to stop the chemical reactions and to avoid
coke formation. This operation is done in two steps. An indirect quenching is first done in
the special exchangers called T L E or TLX (transfer line exchangers) used as steam
generator. Then a direct quenching is done by injection of quench oil at the quench ring

-

the separation of the heavy fractions of the furnace effluents obtained at the bottom of the
primary fractionation tower, the gasoline fraction and lighter fractions as well as the
process steam at the top

-

the condensation of the heavy gasoline fraction as well as the process steam within the
-

water quench tower or scrubber. The light C6-C5 cracked gases come out at the top.
a - Characteristics of cracking or pyrolysis furnaces
In the steamcracking process, the reactions take place within the furnaces. These furnaces act as
chemical reactors. They have varied technologies. The diagram in Figure n°4 shows the most
common geometry.
• General

architecture

The hydrocarbon feed of a furnace is divided into several flows as a function of the number of p a s s e s
of the furnace, generally four to eight.
The naphtha feed enters the furnace at its upper part called the convection zone at about 140°C, and
continues to be heated and starts to vaporize in a first bank of tubes. Leaving the furnace, each pass is
then fed with the dilution steam needed for the process.

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The lower bank of the convection zone that transports the steam-hydrocarbon mixture allows for a
temperature of about 600°C leaving the convection zone.
The intermediary bank of the convection zone allows for independent recovery of heat either for
preheating the boiler feed water before feeding the steam drum or for superheating the steam.
The diagram below shows a cross section of a pyrolysis furnace (figure 1). We distinguish three banks
of the convection zone.

Figure 1

Figure 2
Naphtha feed

Feed

Water or

Boiler
feed

Inlet

• -

O

water

Outlet

< -•

o

vapor

Dilution @

|

steam
inlet

Feed +
vapor

0

Burners
Q .

?

m

I
Dilution steam-hydrocarbon
mixture to radiation

Figure 2

shows the parts of these banks and indicates that the steam-hydrocarbon mixture leaving the

convection zone then goes to the

radiation zone forming

the lower part of the furnace. It is also seen

in figure 1.

A

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This zone is the cracking zone in the strict sense. The cracking tubes are arranged vertically in order to
allow for violent but often indirect heating by the burners. The tubes form pins, some arrangements of
which are shown below.

3-pin coil
tubes of same diameter

Coil with tubes
of increasing diameter

Single vertical tube

Millisecond furnaces

Conventional furnaces

The burners are generally placed on the vertical walls of each side of the tubes. In this case, they are
usually radiant burners. They use gas and the flame is directed toward the wall on dry sand which, at
high temperature, transmits the heat to the tubes by radiation. The walls of the furnaces have 8 to 10
rows of gas burners. It is not rare to find one hundred per furnace.

In some cases, we also use fuel oil burners placed

on the bottom

at the base of the furnace. Given

the desire to lower the nitrogen oxide content of the smoke, gas burners on the bottom now seem
preferable.

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• Problems associated with cracking tubes
Furnaces now have vertical tubes that are better arranged that the old horizontal tube furnaces to
withstand the particularly severe conditions of cracking that can lead to phenomena:
-

of creep, or slow elongation of tubes due to the effect of temperature. The tubes can
withstand skin temperatures on the order of 1000 to 1200°C and become elongated little by
little over time.
The metals chosen must be resistant to creep. The vertical tube furnace technology allows
for placement of tube supports outside of the radiation zone (figure 1) to protect them from
the radiation of the flame;

-

of carburization of the tubes which, at high temperatures, corresponds to enrichment in
carbon of the metallic tube from its inside surface in contact with the hydrocarbons and
coke.
The carbon diffuses or migrates within the alloy, modifies its chemical structure and alters its
mechanical resistance;

-

of erosion caused by the very high speed of the gases;

-

of fatigue due to the repeated thermal cycles during the various operation phases.

These very demanding conditions require the use of heavily alloyed steel containing 25 to 30%
chromium, 20 to 35% nickel, 0.4 to 0.5% carbon as well as other elements such as silicon to
improve resistance to carburization and creep.
The condition of the inside surface of the tubes is also an important factor for pyrolysis and coke
formation conditions as well as for tube carburization.

• Coke formation mechanism • Decoking
The typical operating conditions for a tube located in the cracking zone are shown in the diagram
below.

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Near the wall, the hydrocarbons have a speed
that is low compared with that which exists in
the axis of the tube. Depending on the
roughness of the inner surface of the tube,
there may even be a zone of near immobility of
the hydrocarbon flow. This leads to formation of
a fluid film in which the temperature of the
hydrocarbon species greatly exceeds the
average temperature recorded which leads to
much greater advancement of the cracking
reactions. This leads to the appearance of
heavy hydrocarbons that are hard to eliminate
and coke that remain "stuck" to the wall of the
tubes.

Starting from the average temperature of the
fluid, the facing diagram shows the change in
temperature in the film of heavy hydrocarbons,

1050°C
Metal

the coke and the metallic wall of the tube.
The speed of coke formation depends on the

Coke

operating conditions of the furnace, which we
often designate with the term severity, a function
of the temperature, the flow or residence time,
the hydrocarbon-steam proportion, and also the
characteristics of the feedstock.

Fluid film
of heavy
hydrocarbons

Coke formation is highly detrimental to furnace functioning:
-

it introduces resistance to the transmission of the heat of the flame to the reaction mixture.
This resistance leads to more intense heating and an increase in the skin temperature of
the tubes, which reduces their working life. We consider for example that each mm of coke
increases the skin temperature by a value on the order of 30°C

-

it reduces the

cross section area for

the products and increases the pressure drop, i.e. the

loss of fluid pressure between the point of entry and the output from the coil
-

it requires regular shutdowns of the furnace for decoking operations. This results in a loss
of production and a thermal cycle that can be harmful to the metal.

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A furnace is decoked when the skin temperatures measured reach the allowable limit (for example
1100°C) or when the pressure drop in the coil becomes too high. It involves establishing steam
circulation within the coked tube and introducing a measured dose of air when the temperature is
sufficient to cause progressive combustion of the coke. The steam acts as a diluent and removes the
heat released by coke combustion.
The temperature of the air-vapor mixture is maintained at 600-800°C during decoking. The oxygen
contact changes from 1 % volume at the beginning of the burning up to 15%.
The decoking is done every few weeks. Units are generally designed for successive decoking of
furnaces.
Decoking takes several dozen hours.
b - The main pyrolysis adjustment parameters
• Notions of severity and selectivity
The severity of the pyrolysis is used to check the degree of transformation of the feed into cracked
products. If we increase the severity of the processing, we increase the cracking of the feed and up
to a certain point we increase the formation of the products sought, i.e. light olefins. Beyond this we
promote the decomposition of these products to form gas and coke.
Severity is the very complex result of the combination of various operational variables for
cracking and cannot be determined directly from these variables. We prefer to detect it from an
analysis of the effluents of the cracking:
-

in the case of cracking of ethane, the severity can be directly expressed by the degree of
conversion of ethane.
=

C2 /C2

We can thus use the ratio

in the effluent of the furnace, this ratio increasing

with the severity.
when the feed is a very complex mixture, naphtha or diesel fuel, we can use:

the notion of K S F (Kinetic Severity Function) introduced by Stone and Webster.
This term is related to the conversion of a reference substance, n-pentane,
because this compound, which is often present in naphthas, is not formed during
pyrolysis from other constituents of the feed. Starting from the nCs contents of the
feed and in the effluents of the cracking furnaces, we can calculate the conversion
of nCs and obtain the value of KSF by figure 1 of Figure n°5. From the KSF,
figure 2 then gives the change in yields of various products as a function of the
severity.

=

the ratio C-|/C3 in the effluents
We see that this ratio increases significantly with the intensity of the cracking.

=

While the quantity of methane C i compared to that of propylene C3 is a factor that gives a good
indication of the severity, it is also useful to have a criterion for the selectivity of the operation. This is
=

often estimated by the ratio ethylene C 2 to methane C-|.

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For cracking furnaces, the parameters that allow for modulation of severity are: temperature,
residence time, total pressure and partial pressure of hydrocarbons.
• Influence of cracking

temperature

The table below shows the influence of temperature and cracking performances of a naphtha with the
following characteristics:

Distillation interval

35-160°C

Chemical composition (% vol)
P

80

N
A

15
5

Dilution steam t/t of feed

0.6

The yields of the main pyrolysis products are expressed in % weight with respect to the feed. The table
=

=

shows the change in severity, selectivity and the ratio C3 /C2 .

Temperature (°C)

Change

Products
815

835

855

Hydrogen

H

0.66

0.74

0.81

Methane

CH4

13.82

15.65

17.40

s>

Ethylene

C H

24.71

27.06

29.17

S

Propylene

C3H6

17.34

16.28

14.44

4.17

3.99

Butadiene

2

2

4

C4H6

4.18

Benzene

C6H6

4.89

5.90

7.08

Gasoline

C5-200

22.64

20.84

20.01

Severity

C1/C =

0.797

0.961

1.205

Selectivity

C =/C1

1.788

1.729

1.676

0.701

0.602

0.495

Ratio

3

2

=

C /C =
3

2

=

We can see that the ethylene yield increases with the temperature but that the same is not true for
propylene. At high temperatures, propylene is cracked in turn and contributes to the increased
ethylene yield. The increase in severity thus obtained leads to a moderate decrease in selectivity and a
=

=

substantial decrease of the ratio C3 /C2 .
We conclude that high severity operation favors ethylene, while low severity operation favors propylene
production.

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• Influence of residence time
The residence time of the feed in the coil is a variable to be considered at the same time as the
temperature. The maximum acceptable severity is determined by the speed of coke formation, which,
in terms of these limit operation conditions, leads to a decrease in residence time when we increase
the temperature. In the 1950's, the temperature limits imposed by the metallurgy for radiation tubes
were compensated for with long residence times of 0.7 to 1 second. The corresponding ethylene yields
were limited to 22-23% for relatively good naphthas.
In the middle of the 1960's, the progress in metallurgy allowed for a decrease in residence time to 0.20.4 second, increasing ethylene yields to 28-29%.

"millisecond furnaces"

In the past few years,

have appeared, with residence times of between 50

and 100 milliseconds (0.05 to 0.1 second) for cracking temperatures reaching 870 to 925°C.
This has led to substantial increases in ethylene yields as seen in the table below.

Cracking of naphtha
% Weight
Conventional furnace

Millisecond furnace

Hydrogen

H

2

0.9

1.1

Methane

CH4

15.8

14.9

Ethylene

C H

28.6

32.2

C3H6

15.0

14.3

Butadiene

C4H6

4.4

3.6

Gasoline

C5-200

21.7

18.9

Propylene

2

4

In practice, the residence time is above all determined by the furnace construction characteristics and it
varies little during operation.
• Pressure and partial pressure of hydrocarbons
A lower operating pressure leads in particular to:
-

easier formation of light olefins

-

reduced coke formation

We therefore seek to work in steamcracking furnaces at
obtained by:
-

maintaining the

output pressure

the lowest pressure possible.

This is

of the furnaces at a value as close as possible to

atmospheric

pressure. This supposes a pressure close to atmospheric pressure at the
suction of the cracked gas compressor and pressure drops that are not too large between
the furnaces and compressor. The pressure in the tubes is, given the pressure drops in the
coils, on the order of 2 bars absolute on average
-

reducing the pressure of the hydrocarbons

by injection of steam. The

vapor dilutes the

hydrocarbons and thereby decreases their partial pressure. It also has a substantial
influence on slowing down coke formation reactions. The injection of steam is determined by
the steam/feed ratio. This ratio must be maintained at a level sufficient to limit coke
formation.

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The table below gives the usual values of dilution as a function of the nature of the feed.

H2O/HC (t/t)

C2-C3-C4

0.3-0.4

Naphtha

0.5-0.6

Diesel fuel

0.6-0.8

• Characteristics of the feedstock
We already know the impact of the nature of the various cracked feedstocks on the structure of the
yields obtained in steamcrackers. For a given feedstock, a naphtha for example, the chemical nature of
the hydrocarbons to be cracked has a substantial effect on the performances of the facility, particularly
on the ethylene yield. Naphthas are often composed of largely C5 and C6 hydrocarbons, i.e. light
naphthas for which the distillation interval is 35-100°C. We also find long naphthas containing C7,
Cs, C9 and C10 hydrocarbons.
The analysis of the naphthas generally includes:
-

the density at 15°C
the sulfur content
the ASTM distillation

-

the total PONA and the breakdown by number of carbon atoms as well as the
n-paraffin-isoparaffin breakdown

The best ethylene yields are obtained with naphthas rich in paraffins. Shorter hydrocarbons and
preferably n-paraffins give the best results.

Standard ethylene yields
(% weight)

C -C3-C4
2

Naphtha rich in nP
Aromatic naphtha

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40-45
30-33
20-27

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In units that can process several different feedstocks, it is interesting to compare the flows needed to
obtain the same production of ethylene. The table below shows the propane-butane-naphtha-diesel
fuel comparison.

Loads (tons)

Hydrogen
Methane
Ethylene

Propane 238

Butane 250

Naphtha 298

5.5

4

4.5

3.5

41.6

55

51.3

43.1

100

100

Diesel fuel 385

100

100

Propylene

63.7

43.3

46.6

62

Butadiene

7.1

8.7

12.5

17.3

Other C4

3.1

17

13.4

18.5

Gasoline

15.8

18.3

55.7

70.9

1.2

3.7

14

69.7

Fuel-oil

Depending on the market, it can be valuable to use some cracking furnace effluents as feeds.
This is true for ethane in naphtha steamcrackers. Ethane is recycled and then cracked in specific
ethane cracking furnaces, thereby contributing to increased ethylene production.
Co-cracking also allows for processing of some recycled hydrocarbons mixed with the naphtha feed.
We can co-crack ethane-naphtha, butane-naphtha or C4 cut -naphtha.

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c - Indirect quenching by exchanger - Direct quenching by injection

The purpose of the Transfer Line Exchanger

(TLE or TLX) is to very rapidly cool down the

Furnace effluent to oil

reaction mixture leaving the cracking furnace,
which requires a furnace-exchanger transfer
tube that is as short as possible. This explains

quenching

the positioning of the heat exchanger above the
radiation zones of the furnaces.

HP steam

These heat exchangers have very special
technology and their use is illustrated in the
facing diagram. Cracked gases pass through
the vertical tubes chilled from the outside by
water under pressure in vaporization. In this
way we generate 100-130 bar steam that is
then superheated before being used as primary
steam in the steam turbines.
The problems with these
Exchanger are essentially:
-

Transfer

Line

the risks of clogging of the tubes that carry
the cracked gases with deposits of heavy
polymers and coke. This requires a
temperature that is sufficiently high for the
cooling water in order to avoid condensation
of heavy products
If we crack heavy feedstocks such as
vacuum distillates, the presence of a large
quantity of heavy compounds in the furnace
effluents rules out the use of this type of
exchanger

-

Water

the maintaining of a sufficiently low
temperature of cracked gases to stop the
cracking process. We generally aim for a
temperature on the order of 400°C leaving
the exchangers. It progressively increases
over time due to clogging and even though
decoking of the furnaces helps decoke the
TLE, it is not perfect. The equipment must
therefore be decoked mechanically using
pressurized water, which means shutting
down the furnace. This operation generally
takes place following the third decoking of
the furnace or when the temperature leaving
the TLE becomes too high (450-500°C).

Furnace effluent
(radiation zone outlet)

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Due to the absence of direct contact between the furnace effluents and cooling fluid of the TLE, this
quenching operation is called indirect quenching.
The temperature at the outlet from the TLE's is still too high to allow for feeding of the downstream
separation columns however.
We inject cold fuel oil into the process flow through a quench device or "ring" in order to continue the
cooling of the gaseous flow and to start the condensation of the heaviest fractions. The mixture
temperature is established at about 180°-220°C.
The fuel used - called quench oil - comes from the bottom of the primary fractionation
cooled down to about 160 to 200°C for this second quenching called direct quenching.

tower.

It is

d • Primary fractionation tower
This first fractionation tower receives effluents from the various furnaces of the facility. Its main
purposes are:

-

to separate the heaviest cracked products: cracking

fuel oil and possibly in some units

cracking diesel fuel

-

to start the circuit of the quench oil, which

is recovered at the bottom of the column.

This tower has few trays, it works at temperatures on the order of 100-120°C at the top and 180 to
220°C at the bottom.
The quench oil circuit is very important in the operation of the facility because it must be designed to
eliminate a large part of the heat held by the cracked gases leaving the TLX.

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The main characteristics of this circuit are the following:
-

very high fuel oil flowrate, reaching 10 to 30 times the flowrate of naphtha
large flowrate of heat to be eliminated: the quench oil is cooled down to about 160°C and
this requires the use of numerous heat exchangers

-

presence of filters to eliminate coke particles that may formed in the cracked products or in
the liquid that goes through the bottom of the column

The fuel-oil-gasoline separation is done by a reflux of gasoline injected at the top of the primary
fractionation tower. The top temperature determines the quality of the gasoline produced.
The fuel-oil is generally stripped before it leaves the facility to eliminate the gasoline fractions that can
be dissolved in order to provide a good flash point.
e - Water quench tower
The head gases of the primary fractionation tower feed at its base the water quench tower. Its
functions are:
-

condensing the dilution steam
cooling the cracked products and condensing the heaviest gasoline fractions

The corresponding heat extractions are obtained with a water quench circuit. Starting from the hot
water obtained at the bottom of the column, this circuit includes the cooling exchangers that bring the
water at the top of the column to 50°C for the first injection and to 35°C for the second.
We thereby recover:
-

the process water that is stripped to eliminate the dissolved impurities (CO2, H2S, etc.)
before being revaporized and used again as dilution steam

-

the heavy fractions of gasoline that are partly recycled in reflux of the primary fractionation
tower. The other part is directed to a gasoline stripper that also recovers inter-stage
condensates of the cracked gases compressor. This stripper revaporizes the gases
dissolved in the gasoline and mixes them with the cracked gases obtained at the top of the
water quench tower

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2-

COMPRESSION ZONE
a - Standard composition of cracked gases
Leaving the water quench tower, the problems involved are problems of separation of the various
products and elimination of impurities that are a nuisance with regard to the specifications of
commercial petrochemical intermediaries.
In the case of naphtha steamcracking with an ethane recracking furnace, the standard composition of
the cracked gases is given in the table below. This table also specifies the goals of the separations to
be done and the nature of the impurities to be eliminated.

% weight
typical value

H

Hydrogen

2

CH

4

C2H4

1.1

Methane

16.2

Ethylene

29.2

Goals and particular problems

Separation of hydrogen with good
purity (95%) for hydrogenation units
Recovery of methane for use as fuel
Purity required for ethylene (99.95%
weight)

C2H2

Acetylene

0.3

C H

Ethane

7.2

2

6

Acetylene
eliminated

to

Ethane to

be

be

separated

recycled

to

or

specific

ethane cracking furnaces
CO

1
0.15

C0 -H S
2

C H
3

6

J

2

Propylene

14.3

Impurities to be eliminated to meet
specifications of various products or
due to catalyst poisoning problems
Purity required for propylene 92% or
99.5%

C H
3

8

Propane

0.5

C3H4

Propyne

1

C3H4

Propadiene

J

0.5

C Cut
4

Gasoline C5.200

Water

Propyne

and

propadiene

to

be

eliminated
8.45

19.8

2.3

Recovery of butadiene
Elimination of acetylenics
Elimination of unstable diolefins
Recovery of benzene
Elimination of water to avoid clogging
at low temperatures by formation of
gas hydrate crystals.

100

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The preceding mixture is available in the gas phase at low temperature and low pressure: some
hundred millibars above atmospheric pressure. The separation of the various products requires a large
increase in pressure to avoid excessively low distillation temperatures that would increase the cooling
costs.
Figure n°6 in appendix shows the vapor pressure curves of light hydrocarbons and specifies the
relationship between the boiling point and the pressure. It shows for example that to separate methane
by distillation at - 100°C it is necessary to obtain pressure on the order of 25 atmospheres.
It also shows that:
-

carbon monoxide CO is slightly more volatile than methane
acetylene is between ethylene and ethane

-

propadiene and methyl acetylene are a little heavier i.e. a little less volatile than propane

Steamcracker product separation systems most often require a pressure on the order of 30-35 bars.
This leads to high energy expenses for compression of the cracked gases.
b - Cracked gas compressor
This is a centrifugal compressor that generally compresses in five stages. A standard installation is
shown in Figure n°7.
The main problems involved in compression are as follows:
-

need to limit the temperatures reached at the discharge of each compression stage to
about 100°C to avoid polymerization of the most reactive unsaturated compounds
(diolefins) and clogging of the machine. An injection of washing oil is generally done with
each suction to prevent the adherence of polymers to the mechanical parts in movement.
This is the main reason why the compression is done in 4 or 5 stages with cooling at each
stage

-

need to recover inter-stage condensates: in the outflow from each stage, the gases are
cooled to about 30°C, which, given the increase in pressure, leads to condensation of water
and hydrocarbons
The liquid condensates are separated from the gaseous phase in inter-stage drums. The
s t

heaviest hydrocarbon condensates (outflow of 1 , 2

n d

and 3

r d

stages) feed the gasoline

stripper. The condensates at the outflow from the last stages are obtained after cooling to
15°C and are stripped in a deethanizer stripper to separate the C ~ recycled in the
2

+

compression train and the C3 sent directly to the depropanizer.
-

use of large quantities of energy for c o m p r e s s i o n : the power required for compression of
the cracked gases is on the order of 10 000 to 15 000 kW for a production of ethylene of
200,000 t/year from naphtha. This substantial power is usually supplied by a condensation
steam turbine supplied by 120 bar steam generated in the transfer line exchangers and
superheated. The adjustment of the compression power to the output and composition of
the cracked gases is obtained by varying the speed of the turbine. The possibilities for use
of low-cost electrical energy lead in some cases to replacement of the steam turbines with
variable speed electric motors. Variations in the cost of energy and consequently that of
steam constantly modify the corresponding economic analyses however.

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c - Gas washing tower
The gas washing tower, generally located between the 3
main functions:
-

to eliminate

hydrogen sulfide

H2S and

r d

and 4

t h

compression stages, has as its

light mercaptans

(RSH) that could have formed

from sulfur compounds of the feed in the pyrolysis furnaces. We also frequently inject

compounds

sulfur

into the coils of furnaces to reduce the formation of CO and CO2 and to slow

down coke formation
-

to absorb

carbon dioxide

CO2 formed by the action of steam at high temperatures on the

coke within the furnace tubes.
Industrial facilities most often have

caustic washing scrubber, with

the gases brought into contact at

about 40°C with diluted solutions but with increasing concentrations of soda as the gases rise in the
tower.

is then eliminated in the form of sodium

in the

form of

Hydrogen sulfide H2S
sodium mercaptides
sodium carbonate.

soluble in the soda solution and

sulfide, mercaptans
carbon dioxide (CO2) in the

form of

To avoid soda carryover, water washing of the gases completes the operation. The temperature and
the concentration of the soda solutions must not be too high given the risks of polymer formation.
In some cases, caustic washing is preceded by amine treatment, which eliminates most of the H2S
when the feedstocks processed by the steamcracker lead to the formation of H2S in large quantities.

d - Cracked gas dryers
Because of the increase in pressure and the decrease in temperature, which reaches 15°C after the
last heat exchanger at the discharge of the compressor, much of the steam present in the cracked
gases is condensed and removed to flash drums.
We can estimate at 0.05% or 500 ppm mass the residual water content or about 30 kg/h based on
output of cracked gases of 60 t/h.
Although is it present in a low concentration, water is a major nuisance because it decreases the
temperature and leads to formation of ice and gas hydrates that, given the pressure, appear as soon
as the temperature falls below 15°C. These gas hydrates result from the association of water and
hydrocarbons in the solid state and appear in the form of voluminous crystals that can cause clogging.
It is therefore essential that the water be eliminated. This is why the flow goes through dryers that
generally have a fixed bed made of small solid adsorbent beads: alumina, molecular sieves.
The water present in the cracked gas is adsorbed selectively on the surface of the solid. As the water
retention capacity is limited, there must be several dryers and a system allowing for regeneration of the
dryer saturated with water.
We generally use
-

three dryers:

two are in service and arranged in series or in parallel
the third undergoes regeneration, which involves eliminating the water held by countercurrent movement of a hot gas

The efficacy of the operation is checked leaving the dryers. Less than

1 ppm mass of water is

required.

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22

3-

COLD ZONE
a - Cold box
The flow leaving the dryers, which no longer contains water, can be cooled down without risk of
hydrate formation. Figure n°8 shows the functional principle for the system used. The exchangerseparation drum set constitutes what we usually call the cold box. The cooling fluids used are:
propylene, ethylene, the methane produced and also the hydrogen produced. The first two cold fluids
are involved in the refrigeration cycles, the principle of which is shown in Figure n°9.
The cracked gases from the dryers are cooled in 5 stages.
• First stage
The temperature of the cracked gases is reduced from 15 to - 36°C by exchangers using propylene
as a refrigerating fluid (propylene allows for a temperature of - 40°C at the lowest). The condensates
obtained are separated in a flash drum. The liquid phase corresponding to the heaviest cracked
gases is sent to the demethanizer, the vapor phase undergoes the second refrigeration stage.
• Second stage
From - 36°C to - 70°C. The ethylene refrigeration cycle is used to cool and partially condense the
gaseous feed to - 70°C (the ethylene cycle allows for - 100°C at the lowest).
The process already described is repeated; the heavy liquid phase supplies the demethanizer, the
vapor phase continues the refrigeration process.
• Third stage
From - 70°C to - 100°C with the ethylene cycle.
• Fourth and fifth stages
From - 100°C to - 125°C then from - 125°C to - 165°C. By heat exchange with the cold products
leaving the facility (liquid methane at very low temperatures and cold hydrogen), we decrease the
temperature to - 125°C and then to - 165°C.
The heat exchanges used are complex and involve Plate exchangers in which several fluids can
exchange heat. These plate exchangers are also used to support the exchangers of the refrigeration
cycles as of the second and third stages.
The last drum, working a t - 165°C, separates:
-

a gas phase rich in hydrogen (about 95%). The gas also contains methane and carbon
monoxide CO (0.15 to 0.7% vol.). After elimination of the carbon monoxide, the hydrogen
flow supplies the various hydrogenation sections

-

00040_A_A

a liquid phase corresponding essentially to methane which, released and vaporized, is
used to produce a cooling fluid within the cold box. The methane is later used as a fuel in
the furnaces

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23

b - Methanator
The carbon monoxide CO present in low proportions in the cracked gases has a normal boiling point
close to - 190°C. Its volatility is close to that of hydrogen. In normal concentrations, the presence of
CO is a major nuisance because this compound is a poison for the hydrogenation catalysts used to
convert the excessively unsaturated impurities of the C2, C3, C4 and gasoline cuts obtained later.
CO is eliminated within a reactor called a methanator in which the methanation reaction involves
having CO react with hydrogen to produce water and methane.
The reaction is

catalyst often

highly

made of

exothermic i.e. it releases a lot of heat and must be done with a specific

nickel (15 to 35%) on alumina.

The operation temperature is on the order of 250°C at the entry to the reactor, requiring heating of the
hydrogen flow from - 165°C to about 250°C. This flow is called the non-methanated hydrogen flow.
The output temperature is higher given the exothermicity of the reaction. We consider that
transformation of 1 % volume of CO to methane leads to a temperature increase of 70°C. The output
flow is called the methanated hydrogen flow. It is cooled in order to condense some of the water
produced and dried by absorbent passage before it can be used.
Beyond controlled transitory situations that can lead to more CO and that therefore require special
attention due to the corresponding increase in exothermicity, the main danger is a possible loss of
adjustment of the cold box. If the temperatures become too high, there is a risk of gaseous ethylene
entering the reactor. This would lead to hydrogenation of ethylene, a reaction that itself is exothermic.
The reactor could get out of control and cause a major accident.

c - Cold separation train
This train is a set of distillation columns used to isolate the various cuts as well as the products
produced by the steamcracker.
The arrangement of the columns differs from one steamcracker to another. It usually includes:
-

a demethanizer: it receives its total feed in the form of four distinct feeds from the bottom of
the first four drums of the cold box. Its role is to separate by distillation:

the C i methane and residual hydrogen at the top

hydrocarbons as of C at the bottom making up the so-called C 2 cut

+

2

Its operating pressure is about 30 bars, leading to:

a negative temperature of - 98°C at the top, which corresponds approximately to
the boiling point of methane under 30 bars in the presence of residual hydrogen

a positive temperature of + 5°C at the bottom

The condensation of the vapors at the top at - 98°C is achieved by the ethylene
refrigeration cycle.
The methane obtained in the reflux drum in the liquid phase is released and vaporized,
producing cold in the plate exchangers of the cold box.

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The gaseous methane obtained in the reflux drum is also used for cold production before
being released in the gas network.
The methane flow is finally available at the output from a low-pressure unit and in the
gaseous phase; it must be recompressed to supply the fuel gas network for the pyrolysis
furnaces.
The four columns mentioned below are presented in Figure n°10.
a deethanizer
+

Its load corresponds to the C 2 cut obtained at the bottom of the demethanizer. Its role is to
separate by distillation:

a C2 cut at the top containing ethylene (= 80%) but also ethane (19%) and
acetylene (1%)

+

a C 3 cut at the bottom

Its pressure is on the order of 24 bars, leading to:

a negative temperature o f - 15°C at the top

a positive temperature of + 74°C at the bottom

The condensation of the top vapors at - 15°C is provided by the propylene refrigeration
cycle.
an ethane-ethylene splitter
It receives the C2 cut from the deethanizer after elimination of the acetylene present, usually
by selective hydrogenation.
The distillation of the ethylene is done under a pressure of about 17 bars and is relatively
difficult because we are seeking a high level of purity.
The column includes one hundred or so trays and yields:


at the top, purged from the reflux drum, a low flow of gaseous hydrogen, methane
and ethylene
at in lateral liquid withdrawal, ten to fifteen trays under the top of the column,
ethylene of the required purity
at the bottom ethane that is recycled to specific ethane cracking furnaces

Given the operating pressure, the top temperature is on the order of - 30°C, requiring a
condenser using propylene as a cooling fluid. The bottom temperature is between - 5 and
-10°C.
a depropanizer
+

+

Its feed is the C 3 cut from the deethanizer bottom to which we add the C 3 cut produced at
the bottom of the deethanizer stripper mentioned for the compression zone. Its role is to
separate:

a C3 cut at the top containing propylene (91%) but also propane (5%) and
propadiene and methylacethylene (4%)

+

a C 4 cut

Depending on the processes, this column works at variable pressures: from 6 bars to 15
bars. These various choices result from problems that occur at the bottom of the column
+

where the C 4 cut reaches relatively high temperatures that promote the polymerization of
the diolefins present.

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A higher pressure leads to higher temperatures and less costly condensation of head
vapors. It accelerates polymerization phenomena however, which clogs the reboiler and
the bottom trays of the column. If this choice is made, the depropanizer often has two
lower zones, each equipped with its reboiler. While one is working, the cleaning of the other
is done and the change of zone is done when the clogging prevents the reboiiing of the
column or clogs the trays.
a propane-propylene splitter
It receives as a feed the C3 cut from the top of the depropanizer after its propadiene and
methylacetylene have been removed by selective hydrogenation.
There can be substantial differences in the characteristics of this distillation column as a
function of the purity sought for the propylene.
Propane and propylene have volatilities that are very close and separation by distillation
requires a large number of trays and heavy energy consumption to obtain high purity
propylene (99.5% points minimum).
*

Highly pure propylene (polymer grade)
The column has 140 to 180 trays and works under a pressure of 16 to 20 bars. The
temperature at the top is on the order of 40°C and allows for use of a water
condenser. The bottom temperature is about 50°C.
In order to reduce energy consumption, we can facilitate the separation by lowering
the operating pressure. This rules out condensation of head vapors with the
refrigeration water and leads to use of a system of recompression of the head
vapors. The vapors thus compressed can be condensed in the reboiler of the
column by providing the heat required for the process. Such a system is valuable in
terms of energy savings but can only be used if the temperature difference
between the top and the bottom of the column is low. The separation is then done
at a pressure of 8 to 9 bars.

*

Low purity propylene (chemical grade)
In this case the column only has 30 to 50 trays. It produces propylene that is about
94% pure and works at a pressure of 16 to 18 bars.

a debutanizer
The last column of a standard train of naphtha steamcrackers, it receives as a feed the C 4

+

4

cut from the bottom of the depropanizer to which the C5 " cut from the bottom of the
gasoline stripper mentioned for the hot zone is added. It produces:

a C4 cut at the top containing mostly 1,3-butadiene, but also isobutene and other
butenes, n-butane and isobutane, and also highly unsaturated C4 compounds. This
cut can be sold as is

+

a C 5 cut at the bottom corresponding to pyrolysis gasoline. This gasoline has a
high degree of instability due to the presence of a large quantity of diolefins and
other polymerizable compounds. Before leaving the steamcracker, this gasoline is
hydrostabilized. We do first stage hydrogenation involving transformation of
diolefins into olefins

A debutanizer has about 40 trays and works under a pressure on the order of 5 bars. The
top temperature is from 45°C to 50°C and allows for condensation with the refrigeration
water or air. The bottom temperature is from 100°C to 120°C and the reboiiing is done by
low pressure vapor.
The environment of the debutanizer is shown in Figure n ° 1 1 .
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26

III -

SELECTIVE HYDROGENATIONS
The main cuts produced by the steamcracker i.e.:
-

the C cut

-

the

-

the

-

the gasoline cut

2

C3 cut
C4 cut

all have highly unsaturated compounds in the raw state, the presence of which in the commercial end
products is undesirable.
We therefore seek to eliminate them. This is most often done by selective hydrogenation of the cuts
mentioned.
While the similarity of the objectives leads to some common points among the processes used, the problems
encountered in each case are specific and each installation, shown in Figure n°12, deserves special
consideration.

1-

COMMON CHARACTERISTICS OF HYDROGENATIONS
a - Chemical hydrogenation reactions
The desired reactions involve hydrogenation, depending on the cuts:
-

of acetylenic compounds to olefins
of diolefmic compounds to olefins
of mixed compounds containing double and triple bonds to diolefins or olefins

The desire to stop at this stage of the hydrogenation reaction, although other substances could be
hydrogenated, makes this a delicate operation. It must be as selective as possible whence the
expression of selective hydrogenations for these purification treatments.
They all in involve releasing of heat. They are highly exothermic, which creates a serious safety
problem in carrying out the process, which must be designed to control the corresponding increases in
temperature.
Secondary reactions, essentially polymerization reactions favored by high temperatures, require that
the hydrogenation reactors work at low temperatures (depending on the hydrogenations involved, the
reactor entry temperatures are on the order of 20 to 120°C).
The need to work at moderate temperatures and the desire to protect some commercial compounds
from hydrogenation during the process requires the use of catalysts for the processing.
b - Hydrogenation catalysts
• General points regarding

catalysts

A catalyst has two main functions:

00040_A_A

-

it provides a proper reaction speed with respect to industrial production constraints

-

it promotes the occurrence of the target reaction to the detriment of other reactions that
could produce by-products or that could breakdown the expected product

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Petrochemisty uses mostly catalysts in the form of porous solids. Depending on the application, these
are sold in the form of small sticks, beads or grains of variable color depending on the nature of the
catalyst.
They are used in reactors in which they are placed on fixed beds. The feeds to be transformed move
through out these beds. The operating conditions may be adjusted to make them able to carry out the
desired transformations.
• Mode of action of a solid catalyst
A catalyst acts by its surface (Figure n°13), which means that a catalyzed chemical transformation
includes the following steps:
-

arrival of feed molecules and their entry in the pores of the catalyst grains

-

depositing of molecules on the surface of the catalyst (adsorption phase)
departure of the new molecules formed from the surface of the catalyst (desorption
phase)
exiting of the molecules from the catalyst grain and removal with the flow of products

-

In order for the chemical transformation to take place, the surface of the catalyst must be active with
regard to the expected reactions. For this, the catalyst must have an appropriate chemical composition,
which may be obtained by playing with the chemical nature of the porous solid itself or by adding active
substances to it.
The surface must also be sufficiently wide and accessible to the products to be processed.
2

The specific surface of a catalyst, which is expressed in square meters per gram (m /g) of catalyst,
characterizes the extent of the available surface. It often reaches high values of up to several hundred
square meters per gram.
The accessibility is related above all to the dimensions of the pores, which must be large compared
with the molecules. It also depends on the presence of certain poisons, one of the most common of
which is coke that is deposited on the surface and which blocks access. The catalyst's activity is
thereby reduced and in order to restore the desired level a regeneration must be done. This involves
elimination of the coke by burning, thereby making the surface of the catalyst accessible once again.
• Characteristics of hydrogenation

catalysts

For this variety of catalysts, alumina is the main porous support used. This material has no
hydrogenating activity. It is obtained by introduction of metals or metal sulfides that constitute the
active species for hydrogenation.
In the case of hydrogenation of the C cut, which takes place in the gaseous phase, we use palladium
2

as the active species. The catalyst contains 0.02% to 0.1 % by weight of this metal.
For hydrogenation of the C3 cut and if this operation is done in the vapor phase, the catalyst described
previously is suitable. If we hydrogenate the C3 cut in the liquid phase however, this gives us greater
cooling possibilities, allowing for the use of a more active catalyst containing between 0.2 and 0.5%
palladium.
The hydrogenation of the C4 cut is generally done in the liquid phase using a catalyst that is similar to
that used for the hydrogenation of the C3 cut in the liquid phase.

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For gasolines, several types of catalysts may be used. These are catalysts containing:
-

palladium (0.3-0.5%): this is chosen only for processing light cuts with very little sulfur. This
catalyst is very active

-

nickel: this metal is dispersed on alumina in a proportion of 10 to 20% by weight. It is
certainly the most commonly used catalyst for hydrostabilization of gasolines. It can be used
to eliminate traces of mercaptans

-

nickel and tungsten sulfides or those of nickel and molybdenum or even those of cobalt
and molybdenum dispersed on alumina. These catalysts are used for treatment of gasolines
with high sulfur content.

The activity of these catalysts is hindered in varying degrees by some compounds called poisons.
Nickel and palladium-based catalysts are poisoned by:
-

carbon monoxide CO
hydrogen sulfide H2S

-

arsenic, lead

In the operation of hydrogenation facilities it is therefore important to take all necessary precautions to
avoid poisoning of catalysts, which could prevent them from playing their role or even shutdown the
facility.

2-

SELECTIVE HYDROGENATION OF THE C2 STEAMCRACKING CUT
a - Feed and products
The table below gives the typical composition of the C2 cut obtained at the top of the deethanizer.

% weight
Ethane

17

Ethylene

82

Acetylene

1

Depending on the cracking conditions, the acetylene content can vary from 0.8% at low severity to
1.6% at high severity.
The acetylene content specifications at the output from the unit are severe; they require:

less than 5 ppm by weight (0.0005%) of acetylene

To reduce the acetylene content of the feed, we do a dilution of it by processing, in mixture for
example, the C2 cut and the reflux from the deethanizer.
The hydrogen used is the gas rich in hydrogen from the methanator. It is thus normally without carbon
monoxide CO and free of water. Its hydrogen content is on the order of 95%, the remaining 5 % being
mostly methane.

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b - Operating conditions for industrial unit
Figure n°14 shows

an example of an industrial C2 hydrogenation unit. It includes three adiabatic type

reactors i.e., without integrated refrigeration.
In normal operation, two reactors are in service, the third, after regeneration, can replace one of the
other two. This system allows for rapid adaptation when it becomes difficult to meet the acetylene
content specification leaving the unit.
The operation of the facility involves, successively:
-

preheating

of the gaseous feed from

- 15°C to the input temperature for the first reactor,

between 40°C and 80°C
-

a

first injection of

hydrogen with a controlled hydrogen/acetylene ratio to only partially

hydrogenate the acetylene present (molar ratio close to 1.2)
-

sending to the first reactor where the exothermic hydrogenation occurs. The output
temperature demonstrates, by comparison with the entry temperature, the exothermicity.
There is a variation of about 35°C for hydrogenation of 1 % of acetylene to ethylene and
25°C for hydrogenation of 1 % of ethylene to ethane

-

intermediate refrigeration to bring down the temperature level to the desired value and to
remove the heat produced

-

a second injection of hydrogen (hydrogen/acetylene molar ratio close to 1.6) before
sending to second reactor where the reaction is completed. This hydrogen is sometimes
mixed by by-pass of the methanator with a low flow of non-methanated hydrogen containing
CO. Carbon monoxide, when it is present in very small quantities, increases the selectivity
of the catalyst and thus preserves the ethylene yield

-

a heat exchange between the hot effluents and the cold feed

-

the cooling of the products and the separation of "green oils" (compounds resulting from
secondary polymerization reactions) in a drum before feeding the ethane-ethylene splitter.
The "green oils" are generally recycled at the bottom of the deethanizer and can be limited
by increasing the hydrogen/acetylene ratio.

-

checking the acetylene content

leaving the reactor. There must be less than 5 ppm of

acetylene in the ethylene produced
In industrial practice, the C2 conversion generally preserves the ethylene yield or even increases its
selectivity even if it doesn't reach 100% remaining above 0% except perhaps at the end of the
catalyst's working life.

00040_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

3-

SELECTIVE HYDROGENATION OF THE C3 STEAMCRACKING CUT
a - Characteristics of the feed - Necessity of dilution and its application
The C3 cut contains significant proportions of two impurities to be eliminated:

propadiene. The

propyne

and

table below gives the typical composition of the raw C3 cut.

% weight
Propane C3
Propylene Cg

+
Propyne C3

Propadiene Cg

3 to 5
85-92

3 to 6

2 to 4

By comparison with the processing of the C2 cut, the C3 conversion must take into account the
following constraints:
-

necessity of controlling the increase in temperature due to the exothermicity of the
hydrogenation reactions that apply here to a larger quantity of impurities

-

possibility of increasing the yield of propylene by selectively processing propyne and
propadiene to make propylene

Control of the operation generally requires working with a feed diluted by the already hydrogenated
cut.
We thereby seek to bring the propyne and propadiene contents to values on the order of 3 to 4% by
weight maximum. This naturally leads to an increase in the feed flowrate processed in the unit. We
generally see a significant increase for propylene however.
b - Characteristics of the process
There are two types of main processes as a function of the physical state of the feed:
-

more recent

liquid

phase processes allowing for easy elimination of reaction heat by

controlled vaporization of the liquid feed in the reactor
Also, continuous washing of the catalyst by a liquid phase allows for easier elimination of
the "green oils" and thereby preserves the selectivity and activity of the catalyst.
-

the more traditional gaseous phase processes work with several adiabatic reactors
(generally two) with intermediary cooling. They require greater dilution of the feed
As elimination of the "green oils" is difficult, more frequent regenerations are needed.

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The diagram for a hydro
-

C3 gaseous

phase facility with a dilution system is shown in

Figure n°15:

the feed is composed of the top liquid from the depropanizer plus the hydrogenated C3
fraction from the dilution circuit

-

after drying and vaporization, the diluted cut receives the 95% hydrogen, with the ratio
carefully controlled. The entry temperature at the first reactor is on the order of 80°C (60 to
100°C), the output temperature is close to 120°C

-

the exothermicity of the reactions is eliminated by intermediary coolants that bring the
temperature to 80°C at the inlet to the second reactor

-

when the hydrogenation is over, the C3 cut is cooled and then processed in a column,
separating the green oils and the C3 dilution cut from the propane-propylene mixture
The "green oils" return with the C3 dilution cut into the feed of the depropanizer and are
+
finally removed with the C

4-

4

cut.

SELECTIVE HYDROGENATION OF THE C4 STEAMCRACKER CUT
This section, when it is present on site, is frequently considered to be outside of the steamcracker. Not
all petrochemical sites have one, some sell their C4 cut as is or they recrack it.
This hydrogenation, although it is not obligatory (even for butadiene 1,3 recovery), does limit recycling
of this compound, which is used for dilution of C4 acetylenics for which an excessive concentration
would lead to explosion risks.

5-

HYDROSTABILIZATION OF STEAMCRACKING GASOLINES
a - Standard composition of steamcracker gasolines (naphtha feedstock)

% Weight

c

4

c

5

c

6

C7
c

8

C+.9

00040_A_A

P-N Saturated

Aromatic
A

Olefins

Diolefins

Total

0.25

0.25

0.5

5.6

3.4

11.00

20.0

2.8

28.0

1.4

2.8

35.0

2.21

13.94

0.34

0.51

17.0

1.2

7.2

0.12

3.48

12.0

7.75

7.75

15.5

11.81

59.89

5.51

25.79

100.0

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These gasolines are very rich in aromatics, especially benzene, and are thus excellent bases for
obtaining aromatic hydrocarbons or commercial fuels.
In the raw state, steamcracking gasolines have the disadvantage of containing significant proportions
of unstable hydrocarbons that can lead to the formation of solid deposits during storage that are often
called gums.
These gums are mostly produced by polymerization of the diolefins present.
Also, and as a function of the feedstock processed in the steamcracker, they contain thiophenic sulfur
compounds or mercaptans that may need to be eliminated.
b - Characteristics of the process
• Nature of the expected chemical

transformations

They involve essentially:
-

elimination of diolefins
These unstable compounds can be treated by hydrogenation but to limit the consumption of
hydrogen and to preserve the olefins, which have a good octane number, it is valuable to
limit the hydrogenation to transformation of diolefins to m o n o olefins.
The standard chemical reaction is the following:

H
CH2 =

CH

-

C =

CH2

+

H2

CH2

=

CH

-

C -

I
CH

+heat

I
CH

3

C diolefin
5

-

CH3

3

C olefin
5

<
o

transformation of some sulfur compounds such as mercaptans
Mercaptans are a nuisance in the use of steamcracker gasolines as fuel bases. These
chemical transformations involve only compounds in very low concentrations in the feed, but
they bring with them constraints for the choice of the catalytic formula to be used. We then
speak of the softening function of the hydrogenation catalyst.

This process, which aims above all to hydrostabilize steamcracking gasolines, must preserve the
valuable chemical species: the aromatics and the olefins.
• Operating conditions • Catalysts
The first constraint for the process comes from the risks of polymerization of diolefins when we
increase the temperature. This leads to working at relatively low temperatures, on the order of 60°C at
the reactor inlet and consequently to using very active catalysts to obtain good reaction speeds.
The choice of the nature of the catalyst is a function of the content of mercaptan type compounds
present in the feed.

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• Control of exothermicity
As in other hydrogenations, the exothermicity of the reactions is a major problem.
The catalyst is generally selective, i.e. it limits hydrogenation to diolefins, but the problem here is the
high concentration of these hydrocarbons in the feed.
These substantial exothermicity problems are resolved by:
-

treatment of the feed in the liquid phase, as its partial vaporization can absorb some of the
heat released in the reactor

-

high dilution of the fresh feed by the hydrostabilized gasoline to reduce the concentration
of diolefins on the catalyst and to thereby limit the temperature increase

-

injection of hydrotreated and cold liquid gasoline in the reactor. This system, called
quench, is efficient and can replace the dilution system or work with it

• Industrial

application

The diagram of Figure n°16 shows the operating scheme for an industrial facility.
The load is characterized by its diolefin and olefin contents measured by MAV (Maleic Anhydride
Value) and by the for (Bromine index).
-

The MAV is a method for measuring the diolefin content using as a reagent maleic
anhydride, which combines selectively with diolefins in standardized conditions. The MAV
expresses in mg/g the number of milligrams of maleic anhydride fixed by a gram of gasoline.
The MAV's of steamcracker gasolines are generally between 80 and 100 mg/g

-

The bromine index measures the olefin content including diolefins. The bromine combines
with the olefinic double bonds as well as with a single double bond in the case of diolefins.
The bromine index expresses in g/100 g the number of grams of bromine fixed by 100 g of
gasoline. The usual values are between 60 and 80 g/100 g of sample

The gasoline to be treated is mixed with fresh hydrogen free of CO and with hydrogen gas from the
recycle loop and the whole mixture is then brought up to a temperature on the order of 60-80°C.
Given the selectivity of the catalyst during hydrogenation, the injection of hydrogen corresponds to a
large excess of hydrogen.
After reaction, the effluents are cooled down and a separator drum is used to obtain:
-

a gas rich in hydrogen corresponding to the excess introduced. This gas is recycled
the liquid hydrogenated gasoline, part of which is recycled as quench for the reactor. This
gasoline is sent for separation processing downstream

With regard to the operation of the facility, the essential quality controls to check are the MAV and the
bromine index of the gasoline. The usual values are
-

00040_A_A

MAV < 1 mg/g
l slightly lower, an excessively low le indicates abnormal olefin hydrogenation
B r

r

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

34

In the case of the use of streamcracker gasoline as a base for fuel manufacturing, these
measurements are in relation with the specifications of commercial fuels. These involve:
-

-

the gum content (current or potential). The corresponding standardized tests involve
oxidizing the gasoline and measuring the size of the resulting gum deposits
the induction period, which measures in minutes the duration of the resistance of the fuel
to oxygen under pressure and with heat

-

the octane number which, to remain sufficiently high, requires that the olefins and
aromatics not be hydrogenated during the operation

As an example, the table below gives the characteristics of a steamcracking gasoline before and after
hydrostabilization.

potential gum
in mg/100g
induction period
in minutes
octane number
clear search

LOAD

PRODUCT

9 000

<15

50

480

98

97

The other use of the pyrolysis gasoline cut is recovery of aromatics and especially benzene. This
requires a new hydrogenation called the second hydrogenation step. It is not part of the
steamcracker unit in the strict sense when it exists on site.
Figures n°17 and n°18 summarize the information for the steamcracker and its environment.

00040_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

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FOf'MM'OK INHUSTW
iFP

t H A l N i N G

STEAMCRACKING

Stability of some hydrocarbons relative to their constituent elements versus temperature

Figure 1

N-hepiane cracking (reaction steps)

Figure 2

Naphtha steam cracking - Pyrolysis and primary fractionation (operating conditions)

Figure 3

Vertical tube steam cracking furnace (general arrangement)

Figure 4

Severity of naphtha cracking (yield interactions)

Figure 5

Hydrocarbon vapor pressure curves

Figure 6

Compression - Washing - Drying (operating conditions)

Figure 7

Cooling hydrogen and methane separation - Methanation

Figure 8

Ethylene-Propylene cryogenic cycles (simplified scheme)

Figure 9

Ethylene and propylene separation and purification (operating conditions)

Figure 10

Debutanizer and gasoline hydrostabilization

Figure 11

Steamcracker separation and purification sections

Figure 12

Solid supported catalyst

Figure 13

Example of C2 cut selective hydrogenation unit (operating conditions)

Figure 14

Example of C3 cut gas phase selective hydrogenation unit (operating conditions)

Figure 15

Pyrolysis gasoline hydrostabilization (operating conditions)

Figure 16

Steamcracking

Figure 17

Naphtha steamcracking (overall scheme)

Figure 18

Naphtha yield grid

Figure 19

05/06/2008

I

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FORMATION INDUSTRIE
IFP

B

TRAINING

STABILITY OF SOME HYDROCARBONS RELATIVE
TO THEIR CONSTITUENT ELEMENTS
VERSUS TEMPERATURE
— Figure 1

^—

© 2008 ENSPM Formation Industrie - IFP Training

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FORMATION INDUSTRIE
IFP

I

N-HEPTANE CRACKING
— Reaction steps —

TRAINING

Cracking of bonds C — C

• Figure 2 —

DEHYDROGENATION

Cracking of bonds C — H
Addition
reactions
DEHYDROGENATION

' ] PRIMARY
\ | CRACKING

o o
© 2008 ENSPM Formation Industrie - IFP Training

enspm

NAPHTHA STEAMCRACKING -PYROLYSIS AND PRIMARY FRACTIONATION

FORMATION INDUSTRIE
IFP

• Figure 3 •

TRAINING

— Operating conditions —
Pressure (bar abs)
0.6 t/t of feed

210

Temperature (°C)

Dilution MP steam
— O HP steam

Flow rate (t/h)

510
440

35
ZO

T
L
X

C

Steam

1

325

Demineralized
water

civ:?,
f820l^V

to other
PASSES

To other furnaces

Effluents
to others
furnace

Cracked gas to
compressor

35
c -

WATER
QUENCH
COLUMN
PRIMARY
FRACTIONATOR

p
p
p

4

50

Gasoline
condensate
from cracked
gas compressor

Gasoline
STRIPPER

P
h
Naphtha f \
r^r
feed
^mS^-U^hA
80

Process water
to stripper

h

Fuel-oil

CRACKING
FURNACE
© 2008 ENSPM Formation Industrie - IFP Training

enspm
FORMATION INDUSTRIE
IFP

H

TRAINING

VERTICAL TUBE STEAMCRACKING FURNACE
— General arrangement —
— Figure 4 —

enspm
FORMATION INDUSTRIE
IFP

B

SEVERITY OF NAPHTHA CRACKING
— Yield interactions —

TRAINING

nC conversion in %
5

90

95

100

KSF
3
2
1.5

F

1

80

85

90

nCc conversion in %

K S F value v e r s u s n pentane c o n v e r s i o n
— Figure 1 —

4
6
Severity KSF factor

Yields v e r s u s severity
— Figure 2 —

© 2008 ENSPM Formation Industrie - IFP Training

• Figure 5 -

Zone 1

: KSF < 1
low severity

Zone 2

: KSF between 1 and 2.5
medium severity

Zone 3

: KSF > 2.5
high and very high severity

BUIUIBJI dji - 8U)snpu| uopuucy fAjdSN3 8002 ©
a 860 odd a

enspm

COMPRESSION - WASHING - DRYING
— Operating conditions —

FORMATION INDUSTRIE
IFP

TRAINING

— Figure 7 -

O

Cracked gas from
water quench

35

column
Water

H 100

STEAM
TURBINE
OR
ELECTRIC
MOTOR

H

th

4 stage

CRACKED
Interstages HC
HC condensates

condensates to
gazoline

stripper

(Figure 3)
Gas

CAUSTIC

9

SCRUBBER
Water
Water make-up

Sodium
•4--\=n

trd fcd-

Molecular sieves
Caustic solution

T

Concentrated
caustic soda
CRACKED GAS

make-up

o

DRYERS
Pressure (bar abs)
Temperature (°C)

< z >

Flow rate (t/h)

y

Cracked gas

4

to DEMETHANIZER
5
Q

condensates
to DEPROPANIZER
(figure 10)
© 2 0 0 8 ENSPM Formation Industrie - IFP Training

enspm
COOLING-HYDROGEN AND METHANE SEPARATION
METHANATION

FORMATION INDUSTRIE
IFP

B

TRAINING

— Figure 8 —
(^)

Qv

240

H -95%

Pressure (bar abs)
Temperature (°C)

9

CO 1500 to 7000 vol. ppm
-165

METHANATION
REACTOR
CO conversion
into methane

I

' Methane
hydrogen

-125

Ethylene

I

60

Methane
hydrogen

J

HYDROGEN
DRYER

n

-100

Ethylene

-100

i

-

®
Water

Hydrogen 95%
to dehydrogenation
unit

-70

>

Ethylene

30

\

JZ
DEMETHANIZER

-36

I

Propylene
35

Methane 98%
to compression
and fuel gas network

%

15

Cracked gas
from dryers

^

+

C 2 cut
+5
© 2008 ENSPM Formation Industrie - IFP Training

to DEETHANIZER

enspm
FORMATION INDUSTRIE
IFP

o TRAINING

ETHYLENE-PROPYLENE CRYOGENIC CYCLE
— Simplified scheme —

Ethylene cryogenic
compressor cycle

— Figure 9 —

Propylene cryogenic
compressor cycle
Pressure reduction

valve

Pressure reduction
^
valve
Water

Process
Fluid

3

3
100

•35

LP liquid ethylene

LP liquid propylene
-29

40

HP liquid ethylene

HP liquid propylene

Temperature (°C)
( ^ )

Temperature (°C)

© 2008 ENSPM Formation Industrie - IFP Training

Pressure (abs bar)

enspm
ETHYLENE AND PROPYLENE SEPARATION AND PURIFICATION

FORMATION INDUSTRIE
IFP

TRAINING

• Figure 10 —

— Operating conditions —
Propylene
( ^ )

-30

Pressure (bar abs)

H , CH recycling
2

|

|

Temperature (°C)

4

18.5

®

H

2

y / / -//////)

130

-33

95%
120

Propylene
C cut
2

•I

HYDROGENATION

ETHANE - ETHYLENE
SPLITTER

j

Recycle ethane to
cracking furnace
H , CH recycling
2

PROPANE
PROPYLENE
SPLITTER

viA and r U
'DROGENATION
"C HYDRO"
3

H

u
2

95%

58

- > Propane
+
- • C cut
4

© 2008 ENSPM Formation Industrie - IFP Training

4

FORMATION INDUSTRIE
iFP n

TRAINING

DEBUTANIZER AND GASOLINE
HYDROSTABILIZATION
— Figure 11 —

© 2008 ENSPM Formation Industrie - IFP Training

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FORMATION INDUSTRIE
IFP •
TRAINING

( ^ )

STEAMCRACKER SEPARATION
AND PURIFICATION SECTIONS

•Figure 12-

Pressure (bar abs)
Temperature (°C)

H

2

• METHANATION
(CO—> methane)
. Drying

FUEL GAS
-30
ETHYLENE
ETHANE

ETHANE to
ETHANE STEAM
CRACKING
FURNACE

SPLITTER

L
C3 CUT

17

42

+ 70

c

PROPYLENE

3

HYDRO

PROPANE

• COMPRESSION
• WASHING OF GASES

CUTC3

+

• DEETHANIZATION

«fr

DEPROPANIZER

03

C4 CUT

80

: l

"cS
CO

c

C

CD
"O

Cracked
gas

cz
o
o

1-3 BUTADIENE

4

EXTRACTION

HYDRO

<x>
CO

DEBUTANIZER

co

rH HOT

B u i '

^

CRACKING

• PRIMARY
FRACTIONATION
w

PROPANE

1

BY STRIPPING
• DRYING

SPLITTER

f

110

HYDRO
STABILIZATION

GASOLINE

PYROLYSIS
GASOLINE

OF GASOLINE

Hi
to GASOLINE POOL
FUEL

• WATER SCRUBBING

© 2008 ENSPM Formation Industrie - IFP Training

enspm
FORMATION INDUSTRIE
IFP

a

TRAINING

SOLID SUPPORTED CATALYST
— Figure 13 —

External surface

<?

Inside surface of the catalyst

2
cb
US
JS
"co
o

M<

1

.R
£

4. \
\ \

Chemica
Chemical
reaction

cn

Adsorbed /' O
reactants.i
1

p
.'

'

P

Elimination of rhe Prorf^ ,
c/

\

CD
-CD

o
Q.

p

A /
/ //

\._

\ Adsorbed
, •'' products

Active site
o
o

© 2008 ENSPM Formation Industrie - IFP Training

enspm
FORMATION INDUSTRIE
IFP

O

TRAINING

. -\

EXAMPLE OF C2 CUT SELECTIVE HYDROGENATION UNIT
— Operating conditions —
Temperature (°C)

— Figure 14 —
Hydrogen 95%

Pressure (bar abs)
REACTOR OVERCOMING
A REGENERATION
OR ALREADY REGENERATED

Hydrogen
Methane
Ethylene
Ethane

© 2008 ENSPM Formation Industrie - IFP Training

enspm
FORMATION INDUSTRIE
IFP

EXAMPLE OF C3 CUT GAS PHASE SELECTIVE HYDROGENATION UNIT
— Operating conditions —

TRAINING

S t e a m

VAPORIZER
+

— Figure 15 —

0

,

-

*

,

Propylene
H 95%
2

% weg
i ht
Propylene
Propane
Methylacetylene (MAC)
Propadiene (PD)

Paladium
based catalyst

90%
5%
3%
2%

DEGREENOILER

CONVERTERS

REFLUX
DRUM
B

-

1

Water

H 95%
2

DEPROPANIZER

C

4

Temperature (°C)

m

TO DE

Pressure (bar abs)
Dilution loop-green-oils recycling

© 2008 ENSPM Formation Industrie - IFP Training

© 2008 ENSPM Formation Industrie - IFP Training

enspm
FORMATION INDUSTRIE
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STEAMCRACKING

TRAINING

•Figure 17 —

PRODUCTS

FEEDS

Hydrogen-methane

/

/•

NAPHTHA (C5-C10)

W

Thermal cracking
of hydrocarbons

at high temperature

:

= 800°C

during a very short time
c
!

5

Pyrolysis

i

0.2 second

OTHER AVAILABLE FEEDS
In presence of steam
under low pressure

Ethane (C )
2

Gasoline
c

10

/
Fuel

GPL(C -C,)
3

Diesel oil (C -C o)
10

* 2-3 bar

2

Typical yield with naphtha

Distillates ( C - C )
20

40

© 2008 ENSPM Formation Industrie - IFP Training

enspm
FORMATION INDUSTRIE
IFP

D TRAINING

NAPHTHA STEAMCRACKING

Figure 18-

— Overall scheme —

recycled Ethane (for cracking)

Methane (Fuel)

Water

QUENCHAND
PRIMARY
FRACTIONATION

Frigories

Steam driving

FUEL
Frigories

Cracked
gases
HYDROGENMETHANE
SEPARATION

COMPRESSION
WASHING
DRYING

Methane
Hydrogen (+C0)
lOOOOOOOOOOOOOOx

C

+

cut

2

Hydrogen
g
©ooooooooooooooooooooo
o
o
o
JE
C /C
2

3

C cut

SEPARATION

C

+
3

3

, HYDROGENATION,
< OF ACETYLENE .

-o-N

2

Ethane

ETHANE/
ETHYLENE
SEPARATION

THYLENE

cut
ooooooooooo

c /c
3

+

PROPANE/
PROPYLENE
SEPARATION

K.

4

SEPARATION

H
•<

C cut
3

C

c /c
4

+
4

cut

+
5

SEPARATION
C cut
4

Gasoline

HYDROSTABILIZATION
OF GASOLINE

© 2008 ENSPM Formation Industrie - IFP Training

-Ci

PROPANE

enspm
FORMATION INDUSTRIE
IFP

TRAINING

•Figure 1 9 -

NAPHTHA YIELD GRID

%

H Y D R O G EEN

wt

ETHANE

10
20
ETHYLENE
NAPHTHA

30

>

C CUT
2

40
ETHANE
50
60

H

PROPYLENE

C CUT
3

PROPANE + PROPYNE - PROPADENE

70 -

1 - 3 BUTADIENE
OTHERS C

80 GASOLINE
90 100 -

C CUT
4

4

FUEL

© 2008 ENSPM Formation Industrie - IFP Training

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

enspm

Refining-Petrochemicals-Chemicals-Engir.eering

r

fi'inMA '.JN 'Nn.lS'R'r
IFP

T R A I N I N G

I

- VOLATILITY: VAPOR P R E S S U R E AND BOILING TEMPERATURE

1

II - FLASH OF HYDROCARBON MIXTURE

2

III - CONTINUOUS DISTILLATION

3

1 - Principle
2 - Industrial features of the distillation process

3
3

APPENDICES
Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7

Hydrocarbon vapor pressure curves
Vapor pressure of water from 5 0 T to critical point
Industrial implementation of a flash separation
Liquid-vapor countercurrent flow
Liquid-vapor contact - Trays
Liquid-vapor contact - Packing
Operating principle of a depropanizer

05/06/2008

J

1

VOLATILITY: VAPOR PRESSURE AND BOILING TEMPERATURE
Distillation, absorption and stripping are all widely used separation processes that differentiate between
the components of a mixture through their volatility.
The difference in volatility between the components of a mixture is often characterized by the difference
between their boiling points or their vapor pressure. These characteristics are shown by the vapor
pressure curves of pure substances.
Vapor pressure curves are plotted on a pressure-temperature diagram. They indicate the physical state of a
pure substance as a function of the prevailing pressure and temperature.

P

r e s s u r e

Normal
boiling point

Boiling point

These curves are used:
-

to determine the temperature of transition from the liquid state to the gas state, at constant pressure.
This is known as the boiling point.
At normal pressure, i.e. at 1.013 bar, it is called the normal boiling point. Figures 1 and 2 in the
appendix give the normal boiling points of the lighter hydrocarbons and water.

-

to determine the pressure at which liquid and vapor phases coexist, at a given temperature and under
storage conditions.
This is known as vapor pressure and it depends on the nature of the liquid product and on the
temperature.

©2008 ENSPM Formation Industrie - IFP Training

2

II -

FLASH OF A HYDROCARBON MIXTURE
The difference in volatility of the components of a mixture is set into evidence in a flash (figure 3).

S333I
Heat
exchanger

(Pi)

Flash
drum

j

»^
o

Pump

o

Q

Flashing (or liquid-vapor separation) is performed continuously and illustrates the difference in volatility of the
components of the mixture.
The lighter or more volatile components tend to be gaseous. Their concentration in the gaseous phase
is higher than in the feed. They have low boiling points and high vapor pressures.
The heavy or less volatile components on the other hand tend to be liquid. Their concentration in the
liquid phase is higher than in the feed. They have high boiling points and low vapor pressures.

OOOO6_D_A

© 2008 ENSPM Formation Industrie - IFP Training

3

III -

CONTINUOUS DISTILLATION
1-

PRINCIPLE
The previously described separation process can be intensified by:
- countercurrent circulation of the two liquid and vapor phases inside a distillation column or
tower
- contact between the liquid and vapor phases through trays or packing. At each step the vapor
becomes richer in light components and the liquid richer in heavy components
The result is a much finer separation of the mixture. The top product or distilled product contains the
light components and in the bottom product or residue are the heavy components. The separation is
much more selective than in the case of simple flash separation.

2-

INDUSTRIAL F E A T U R E S O F T H E DISTILLATION P R O C E S S
The liquid-vapor countercurrent flow requires:
-

a condenser to initiate the liquid flow in the column via the external reflux entering the
top of the column

-

a reboiler to initiate the vapor flow by partial vaporization of the liquid at the bottom of
the column

The partially vaporized feed enters the column roughly at the half-way mark and thus also contributes
to these two flows (Figure 4).
The liquid-vapor contact is achieved:
-

by trays: the vapor flows up through the valves and contacts the horizontally flowing
layer of liquid (figure 5)

-

or by packing: the liquid flows over the rings or saddles and forms a film which is
contacted by the rising vapor (figure 6)

The operating conditions of an industrial column - in this case a depropanizer - is shown in Figure 7.
-

The operating pressure is fixed by the operating conditions prevailing in the reflux
drum, i.e. the vapor pressure of the overhead liquid product. It then remains fairly
constant throughout the column.

-

The temperatures in the column are the boiling points of the circulating products:

the overhead temperature is the lowest and is that of the light components
drawn off from the top of the column

the bottom temperature is the highest and is that of the heavy products leaving
the bottom of the column

The variation in temperature throughout the column corresponds to the changes in
composition that occur from one tray to another.
-

00006_D_A

The flow rate of the external reflux and the amount of heat required by the reboiler
depend on the desired quality of separation.

©2008 ENSPM Formation Industrie - IFP Training

-200
I

DPPC010B

-150

-100

-50

0

50

100

150

200

enspm
FORMATION INDUSTRIE
IFP

n

TRAINING

VAPOR PRESSURE OF WATER
FROM 50°C TO CRITICAL POINT
• Figure 2 —
500
400

Critical
point

300

t C |

221.29 bar *

CD

aZ
200

374.15 °C
100
90
80
70
60
50

A

7\

z

40
30

20

V\
10
9
8
7
6
5
4

f'Tl

1
0.9
0.8
0.7
0.6
0.5

u

iiHJ

0.4
0,3

0.2

0,1

i
50

100

150

200

250

© 2008 ENSPM Formation Industrie - IFP Training

300

Temperature (°C)
P
i »'i m
T

350

400

© 2008 ENSPM Formation Industrie - IFP Training

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FORMATION INDUSTRIE
IFP

B

TRAINING

LIQUID-VAPOR COUNTERCURRENT FLOW

OVERHEAD
LINE

/SHHHHHHHHHHHHHBH^
j^j

Vaporisation of
/ external reflux

jj*
g

• Figure 4 -

Overhead vapor
Cooling
fluid

External reflux
CONDENSER
Condensation
of interna
reflux
REFLUX
DRUM

Internal
reflux

njection of partially
vaporised feed into
quid and vapor
flows

Vapor
produced
by the
reboiler

Heating
fluid
Partial
vaporisation
Column
bottom
liquid

© 2008 ENSPM Formation Industrie - IFP Training

© 2008 ENSPM Formation Industrie - IFP Training

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FORMATION INDUSTRIE
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B

TRAINING

LIQUID-VAPOR CONTACT
— Packing —

Structured packing

— Figure 6

enspm
FORMATION INDUSTRIE
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TRAINING

• Figure 7 -

OPERATING PRINCIPLE OF A DEPROPANIZER

Temperature (°C)
Pressure (bar)
>

© 2008 ENSPM Formation Industrie - IFP Training

Flowrate (t/h)

enspm
If-P •

Refining-Petrochemicals-Chemicals-Engineerlnci

T R A I N I N G

I

-

LIMITS OF STANDARD DISTILLATION

1

II -

PRINCIPLE OF EXTRACTIVE DISTILLATION

2

III -

MAIN PETROCHEMICAL APPLICATIONS

3

IV -

MODE OF ACTION OF THE SOLVENT

4

V -

THE MAIN EXTRACTIVE DISTILLATION SOLVENTS

5

DT EXT-00535 A A-Rev. 1
Z_z


. „
,
,. . . . .
,
. .
© 2008 ENSPM Formation Industrie - IFP Training
o

n

r

i

n

i

i

r

r

n

T

05/06/2008

1

LIMITS OF STANDARD DISTILLATION
We know that distillation is a separation process based on the differences in volatility between the
constituents to be separated.
The feasibility of such an operation depends on the boiling points that often characterize the volatilities having
a sufficiently large difference to make separation possible. If the boiling points are too close together,
separation becomes difficult or impossible. We also know that some constituents of mixtures have very close
volatilities in some conditions due to non-ideality.
Many examples from petrochemistry can be taken to illustrate these separation difficulties.
The tables below show, for benzene and butadiene, the nature of constituents that have similar boiling points
that make standard distillation impossible.

Boiling point (°C)

Boiling point (°C)
Isobutene

-6.9

1-butene

-6.3

1,3-butadiene

-4.4

n-butane

-0.5

Methylcyclopentane

71.8

Benzene

80.1

Cyclohexane

80.7

We see that benzene is theoretically inseparable from cyclohexane. We also know that benzene-hexane and
benzene-n-heptane separations are very difficult.
Also, 1,3-butadiene, an important petrochemical intermediary, is surrounded by other very close C4
hydrocarbons, especially isobutene and 1-butene.
Separation by standard distillation therefore seems impossible in both cases, even if we use columns with a
very large number of trays.
If the constituents to be separated belong to different chemical families, it is possible to force the
distillation by using a solvent in mixture with the products processed. The role of the solvent is to modify the
natural volatilities based on the differing affinities of the compounds in the liquid phase.
We thereby artificially create a difference in volatility which makes separation possible by distillation which is
then called extractive distillation.
Extractive distillation is thus a forced distillation using a solvent to modify the volatilities and to make
separation

i_A_A

possible.

©2008 ENSPM Formation Industrie - IFP Training

2

II -

PRINCIPLE OF EXTRACTIVE DISTILLATION
Starting with a mixture of several substances marked a, b, c, d, e, with similar volatilities, the diagram below
shows the effect of a solvent S. The volatilities in the presence of solvent become very different and the
heaviest compound, apart from the solvent, is the one we seek to separate.

+ Volati

+ Volatil
r

e

a

k.

c

k.

d

t

Distillate
or raffinate

^r
V

(

\

41

-b

«

Residue
or
extract

f

-S

Natural volatilities
without solvent

Volatilities
in the presence
of a solvent

The new arrangement of volatilities allows us to do a first separation marked ®
to:
-

on the diagram and leads

a distillate or raffinate including the volatile constituents in the presence of solvent (a-c-d-e)
a residue or extract in which we have constituent "b" which was sought and the solvent (b-s)

This first separation is most often done in a single extractive distillation column.
Then of course, "b" and "S" must be separated in a standard distillation column often called a "stripper" or
solvent regenerator (separation ©).
The scheme for a typical extractive distillation system is shown below. The regenerated solvent obtained at
the bottom of the stripper is recycled after exchange of heat to the extractive column where it is injected near
the top of the column so that it is present in the internal reflux. The trays above the solvent entry point aim to
limit solvent losses in the distillate.

00535_A_A

©2008 ENSPM Formation Industrie - IFP Training

3

III -

MAIN PETROCHEMICAL APPLICATIONS
Extractive distillation is a process that is widely used in heavy petrochemistry to purify certain large olefinic or
aromatic intermediaries. The main applications include:

00535_A_A

-

separation of 1,3-butadiene from a C4 steam cracking cut

-

separation of benzene from a C6 steam cracking cut

-

separation of xylenes from Cs compounds in a heavy reformate

-

separation of acetylene from a C2 steam cracking cut

-

recovery of a benzene-toluene cut in a light reformate

© 2008 ENSPM Formation Industrie - IFP Training

4

IV •

MODE OF ACTION OF THE SOLVENT
The solvents used in extractive distillation are, as we saw, polar compounds. The solvent molecules are
electrically neutral overall, but act as real little electric dipoles.
This polarity is due to the presence of oxygen or nitrogen atoms within the solvent molecules.
As a function of this polarity, the molecules with the lowest non-ideality with the solvent are those which are
the most polarizable. Their volatility is not greatly affected by the solvent.
On the contrary, the non- polarizable molecules have a strong positive non-ideality with the solvent and thus
have a sharp increase in their volatility.
The polarizability of a molecule determines the forces of interaction that it will show in the liquid phase with
the solvent molecules.
These solvent-polarized molecule forces of attraction lead to retention of these molecules in the liquid phase.
These forces of attraction are much weaker for non-polarizable molecules. These are therefore less
maintained in the liquid phase.
The tendency to polarization is linked to the degree of non-saturation of the molecules. The scale below gives,
comparatively, the behavior of the various families of hydrocarbons.

Paraffins

Naphtenes

Aromatics
Olefins

Diolefins

Acetylenics
>

Less
polarisable
molecules

= important
non ideality

More
polarisable
molecules

= lean
non ideality

Depending on the case, we see that extractive distillation solvents can extract the most unsaturated
compounds: olefins, aromatics, diolefins and acetylenics.

00535_A_A

©2008 ENSPM Formation Industrie - IFP Training

5

V-

THE MAIN EXTRACTIVE DISTILLATION SOLVENTS
Industrial experience in heavy petrochemistry limits the range of extractive distillation solvents to some
compounds which are widely used, although the list below is not exhaustive. Some of these solvents are also
used in liquid-liquid extraction.

NMP, N-methyl pyrolydone is used pure for extractive distillation of benzene, and in aqueous solution for
separation of butadiene. We also find it as a liquid-liquid extraction solvent for aromatics.

CH

- CH

2

I

Boiling point 204-209°C

2

I

CH

C

2

=0

M=99 kg/kmol
1 5

d

CH

4

=1.03

3

ACETONITRILE is widely used mixed with water for extractive distillation of butadiene

Boiling point 80-82°C
M=41 kg/kmol

CH -C=N
3

1

d/

=0.788
ISA A

D.M.F., dimethyl formamide

CH

3

A" V O

Boiling point 153°C

H

M=73 kg/kmol

N-C
/
W
CH
0

df

3

=0.44

D.M.A., dimethyl acetamide

CH

Boiling point 165-168°C

3

CH - C-N
II
\
0
CH

M= 87 kg/kmol

3

3

d

A

=0.937

To better define the functioning characteristics for this type of process, we will look below at two important
extractive distillation processes situated quite often in ethylene plants:

00535_A_A

-

separation of benzene from hydrogenated C6 cut

-

extraction of 1,3-butadiene from C
4 cut

©2008 ENSPM Formation Industrie - IFP Training

enspm
irt>

Refining-Petrochemicals-Chemicals-Engineering

T R A I N I N G

VARIOUS ROUTES FOR C4 CUT UPGRADING

I

-

II -

RECOVERY OF BUTADIENE

1

1 -

Composition of the crude C4 steamcracking cut

1

2

-

Problems related io recovery of 1,3-buiadiene

2

3

-

Hydrogenation of C4 cut

2

4

-

Extractive distillation and superfractionating

3

USES OF RAFFINATE 1 AND RAFFINATE 2

5

Figure n°1: Hydrocarbons present in the C4 cut
Figure n°2: C4 cut hydrogenation- Operating conditions
Figure n°3: Volatility modification by solvent introduction
Figure
Figure
Figure
Figure

n°4: Butadiene separation by extractive ditiliation - Solvent: acetonitrile (ACN)
n°5: Butadiene separation by extractive ditiliation - Solvent: acetonitrile
n°6:1.3-Butadiene separation by extractive distillation - solvent: NMP
n°7: C4 cut upgrading

05/06/2008

J

1

I•

RECOVERY OF BUTADIENE
1 -

COMPOSITION OF THE CRUDE C4 STEAMCRACKING CUT
The C4 cut from the top of the debutanizer includes hydrocarbons with four carbon atoms:
-

paraffins (n-butane; isobutane)
olefins (isobutene; 1-butene, cis 2-butene, trans 2-butene)

-

diolefins (1,2-butadiene and 1,3-butadiene)
acetylenics and other highly unsaturated compounds (1-butyne or ethylacetylene EAC;
vinylacetylene VAC)

Figure n°1 gives the characteristics of these compounds. In particular, it shows the similarities in
volatility between these hydrocarbons.
The table below gives, by family, the typical proportions of various hydrocarbons in C4 leaving the
steamcracker debutanizer.

C Cut
4

% mass

• Paraffins
n-butane

<5

iso-butane

<5

• Olefins
isobutene
1-butene
2-butenes

20-35
10-15
5-10

• Diolefins
1,3-butadiene
1,2-butadiene

35 to 55
0.1

• Acetylenics
MAC methylacetylene
VAC vinylacetylene
EAC ethylacetylene

0.01 to 0.5
0.3 to 1.5
0.2

We see the large proportions of 1,3-butadiene and isobutene in this cut.

00044_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

\

,
I
J

r

2

2-

PROBLEMS RELATED TO RECOVERY OF 1,3-BUTADIENE
1,3-butadiene is expected to be extract with minimum 99.6% purity by weight from this cut to be used,
alone or with other compounds, to make various kinds of rubber by polymerisation.
In practice however we face two problems:
-

the nature of the separation process to be applied. Because of the small differences in
volatility of the compounds in the C4 cut, standard distillation cannot be used. Extractive
distillation is used industrially with a solvent that interacts with 1,3-butadiene.

-

the presence of acetylenics in the C4 cut. These compounds and to a lesser extent some
olefins unfortunately interact with the solvent. In order to obtain very pure 1,3-butadiene, we
must superfractionate the crude 1,3-butadiene extracted. This operation involves a standard
distillation but in a train of columns with a large number of trays. This separation then
produces a heavy cut that concentrates the acetylenics in C4. However, an excessive
concentration of acetylenics leads to explosion risks. We therefore dilute the heavy cut,
leaving in the 1,3-butadiene.

3-

HYDROGENATION OF THE C4 CUT
This hydrotreatment, while not obligatory, limits the quantity of 1,3-butadiene needed for dilution of the
acetylenics. In these conditions the hydrotreatment done optimizes the rate of recovery of commercial
butadiene. Also, hydrogenation of the impurities keeps the feed quality of the extractive distillation
more or less constant.
a - Characteristics of the reactions carried out
The hydrogenation reactions done are transformations of the impurities in C4 (1,2-butadiene, 1-butyne
or ethylacetylene, vinylacetylene) into butenes for the most part, and to a lesser extent 1,3-butadiene.
This compound, commonly found elsewhere, can be easily hydrogenated. This requires the use of a
selective catalyst. All of these reactions produce heat.
The high degree of unsaturation of the C4 cut also leads to C6-C12 by-products from polymerization
reactions.
As these reactions are favored by high temperatures, it is necessary to work at lower temperatures,
b - Application - Operating conditions
Figure n°2 shows a hydrogenation section of the C4 cut. The cut to be processed supplies the first
reactor, generally in the liquid phase. This ensures that it benefits from constant washing with the
palladium-based catalyst used to eliminate the polymers formed, and also minimizes the increase in
temperature in the reactor by partial vaporization of the reaction effluent.
The input temperature for the first reactor is between 20 and 40°C. The output temperature is a
function of the pressure level, which is generally set between 7 and 12 bars.

00044_A_A

© 2008 ENSPM Formation Industrie - IFP Training

3

The second reactor works at an almost constant temperature equal to that of the output from the first
reactor if there is no intermediary refrigeration. In this example, the temperature stabilizes around 60°C
with a pressure of 11 bars.
The hydrogen used is generally 95 % methanated hydrogen.
In this case, the load is diluted by recycling of the hydrotreated effluent following elimination of the
polymers formed.
The hydrotreated C4 cut, with the most unsaturated compounds partially eliminated, can supply the
1,3-butadiene recovery section.

4-

EXTRACTIVE DISTILLATION AND SUPERFRACTIONATING
The extractive distillation done produces:
-

raffinate 1, which contains: n-butane, isobutane, isobutene, 1-butene, most 2-butenes
crude extracted 1,3-butadiene

This latter flow has a different composition depending on whether the extractive distillation is in one or
two steps.
The associated diagrams are as follows.
• Extractive distillation in one step

• • Raffinate (Butanes, Butenes)

This system usually uses acetonitrile as a solvent. Figure n°3 shows the changes in volatility caused
by the solvent. Figure n°4 shows the corresponding extraction column. Figure n°5 shows the
extractive distillation column in its unit environment.

00044_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

4

• Extractive distillation in two steps

* Raffinate 1 (Butanes, Butenes)

C4 steam
cracking cut

C

4

hydrogenation

Extractive
distillation
column (7)
-> Light (MAC)

Classic
distillation

Recycle acetylenics

Extractive
distillation
column (2^)

Crude, extracted
1,3-butadiene

This system usually uses a N-methylpyrolidone
corresponding extraction system.

00044_A_A

Very pure
1,3-BUTADIENE

-> Heavy
(2-Butenes, 1,2-Bd)

(NMP) type solvent. Figure n°6 shows the

© 2008 ENSPM Formation Industrie - IFP Training

5

II -

USES OF RAFFINATE 1 AND RAFFINATE 2
As raffinate 1 contains a proportion of isobutene of between 40-50%, it is valuable to use this compound. It
can be:
-

upgraded on line on a MTBE unit
extracted for another chemical use

If we draw off the isobutene, we are left with a residual C4 cut called raffinate 2 that contains butanes and
butenes.
The majority compound at this point is 1-butene. Its separation by superfractionating is rarely done.
We can however comprehensively use the butenes that are still present. One possible use of raffinate 2 for a
petrochemical complex associated with a refinery with an alkylation unit is additional feeding of this refining
unit. Figure n°7 shows various possibilities for using the C4 cut.

00044_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

FORMATION INDUSTRIE
IFP

B

TRAINING

HYDROCARBONS PRESENT IN THE C4 CUT

Figure n°1 —

Constituents

Ac

General formula

Propyne or methyl-acetylene

Developped formula

Normal bp
(°C)

sp.gr

1 5
4

C3H4

-23.2

0.620

MAC
P

Isobutane

C4H10

-11.7

0.563

0

Isobutene

C H
4

8

-6.9

0.600

0

Butene-1

C H
4

8

-6.3

0.601

diO

Butadiene 1-3

C H

6

-4.4

0.627

P

n-butane

C H

1 0

-0.5

0.585

0

trans-butene-2

C H
4

8

+ 0.9

0.610

0

cis-butene-2

C H

8

+ 3.7

0.627

Ac

Vinyl-acetylene (VAC)

C4H4

+ 5.1

Ac

Butyne-1 (EAC)

C H

+ 8.1

Ac

Diacetylene

C4H2

diO

Butadiene 1-2

C H
4

6

Ac

Butyne-2

C H

6

4

4

4

4

4

****

6

0.650

+ 10.3

*****

P: Paraffins
O: Olefins
diO: Diolefins
Ac: Acetylenics and other highly unsaturated compounds

© 2008 ENSPM Formation Industrie - IFP Training

+ 10.8

+ 26.9

0.657

enspm
FORMATION INDUSTRIE
IFP

C4 CUT SELECTIVE HYDROGENATION UNIT

TRAINING

5-

JL

— Operating conditions —
V-~-o
• Figure 2 -

Temperature (°C)
Pressure (bar abs)

DEBUTANIZER
REFLUX DRUM

Debutanizer

© 2008 ENSPM Formation Industrie - IFP Training

FORMATION INDUSTRIE
IFP

»

TRAINING

VOLATILITY MODIFICATION
BY SOLVENT INTRODUCTION
— Figure 3

Natural volatilities

Volatilities in presence
of solvent

A C N : Acetonitrile

© 2008 ENSPM Formation Industrie - IFP Training

enspm
FORMATION INDUSTRIE
IFP

M TRAINING

BUTADIENE SEPARATION BY EXTRACTIVE DISTILLATION
— Solvent; acetonitrile (ACN) —
• Figure 4 •

Temperature (°C)
Pressure (bar abs)
Xs

% weight

Solvent
ACN + 7% to 10%
weight water

X » 80°y
S

Feed
vaporizer

t/h
anes

0.5

1-ene

4.03

2-enes

0.77

1,3-BD

Raw 1,3-butadiene
to
superfractionating

8
5:30

SOLVENT
t/h
Butanes

0.5

1-Butene

4.03

2-Butenes

0.9

1,3-Butadiene

4.5

Acetylenics

0.07
10.00

REGENERATION

X ^70%
S

t/h
2-enes

0.13

1,3-BD

4.5

Ac

0.07

ACN

55.48

water

4.42
64.60

^333533 X5 3 95%

"""""
Solvent
make-up

© 2008 ENSPM Formation Industrie - IFP Training

enspm
FORMATION INDUSTRIE
IFP

TRAINING

BUTADIENE SEPARATION BY EXTRACTIVE DISTILLATION
— Solvent: Acetonitrile —
• Figure 5 •

Solvent purge
WATER
SCRUBBINGI
* - p \ I 1,-3 butadiene
topping

n P

5

1,-3 butadiene
tailing

© 2008 ENSPM Formation Industrie - IFP Training

enspm
FORMATION INDUSTRIE
IFP

a

TRAINING

1,3-BUTADIENE SEPARATION BY EXTRACTIVE DISTILLATION
— Solvent: NMP —
FY

Temperature (°C)

\ \ nr

Pressure (bar abs)
<(

)> Flow rate (t/h)

Solvent (NMP + water)

C

2

COLUMN

(NMP + water)

C-| column
butanes

'
top

1- butene
Feed
C4 cut

2- butenes

<
sidestream

1,3-butadiene

T
bottom

acetylenics
solvent

Raw 1,3-butadiene
to superfractionating

,r
C2 column

Volatility

2-butenes

scale

'

butanes

1,3-butadiene

1- butene

acetylenics

tc>P

bottom

2- butenes
solvent

1,3-butadiene
acetylenics

° 3
C COLUMN

solvent

3

1,3-butadiene
+

Diluted acetylenics

acetylenics

( j D

80
Solvent
+
1,3-butadiene + acetylenics

© 2008 ENSPM Formation Industrie - IFP Training

C3 column
1,3-butadiene t top
acetylenics

i|sidestream

Solvent

^bottom

enspm
FORMATION INDUSTRIE
IFP

TRAINING

C4 CUT UPGRADING
Raw C4 cut
st

C> • 1 treatment
• Figure n°7 -

nd

• 2 treatment
Upgraded
products

^

Other
treatments

RAW C4 CUT

1,3-BUTADIENE
AND BUTENES
SELECTIVE
HYDROGENATION

ACETYLENICS
PARTIAL
HYDROGENATION

1,3-BUTADIENE
AND BUTENES
HYDROGENATION
INTO BUTANES

EXTRACTIVE
DISTILLATION

Raffinate 1

Raffinate 1 bis

7

SUPERFRACTIONATION

1

i>

ALKYLATION

i

i

Q

-t

Raffinate 3

BUTENES
ISOMERIZATION
INTO ISOBUTENE

I

BUTENE1

© 2008 ENSPM Formation Industrie - IFP Training

SELECTIVE
HYDROGENATION OF
1,3-BUTADIENE
HYDROISOMERIZATION
OF BUTgNE 1
INTO BUTENES 2

enspm
If-p" •

Refining-Petrochemicals-Chemicals-Engineering

TRAINING

NATURE OF AROMATIC HYDROCARBONS.
SOURCES AND ASSOCIATED PROCESSES

I

-

II -

III -

IV -

V -

I

PRESENTATION OF THE MAIN AROMATIC COMPOUNDS

1

1 2 3 -

1
2
2

Benzene
Toluene
Cs Aromatics: ethylbenzene, xylenes

MAIN SOURCES OF AROMATIC HYDROCARBONS

4

1 -

Catalytic reforming

4

2
3

Steamcracking
Coking plant benzols

8
9

-

THE MAIN PROCESSES FOR TURNING T X INTO B.T.X

10

1 -

Hydrodealkylation of toluene into benzene

10

2

-

Dispropornation of toluene

11

3
4

-

Transalkylation
Isomerization of xylenes

12
13

MAIN SEPARATION PROCESSES USED TO OBTAIN AROMATICS

14

1 -

Aromatics - non aromatics separation

14

2

Separation of an aromatic from other aromatics

17

-

STANDARD SCHEMES FOR SEPARATION AND PURIFICATION OF AROMATICS

20

1 2 3 -

20
21
22

Treatment of reformates
Treatment of steam cracking gasolines
Treatment of benzols

P C ARO - 00045_A_A - Rev. 2

© 2008 ENSPM Formation Industrie - IFP Training

05/06/2008

I

1

PRESENTATION OF THE MAIN AROMATIC COMPOUNDS
Aromatic compounds have a characteristic structure called a benzene ring in which 6 atoms of carbon
forming a hexagonal ring are linked by the equivalent of 3 single bonds and 3 double bonds.

For each carbon atom
2 single bonds
1 double bond

In fact the six carbon-carbon bonds are equivalent and in between single bonds and double bonds. For this
reason, the representations below are often used:

or

I
The aromatics are, with the paraffins and naphthenes, the third large family of hydrocarbons present in crude
oil. These compounds are derived from benzene C6H6, the first of the aromatic hydrocarbons.

1-

BENZENE
The corresponding molecule is shown below:

Benzene CqHq

bp = 80.1°C
spgr = 0.884

I5_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

2

Benzene is an essential raw material in petrochemistry. Figure 1 shows the ways to obtain it and
its main uses. Benzene is also present in gasoline. The benzene content of European unleaded
gasoline is strictly limited however because of its toxicity.
The aromatic hydrocarbons have at least one benzene ring that gives them particular properties.
Derivatives are obtained by substitution of the hydrogen atoms of benzene with: methyl (- CH3),
ethyl (- C2H5) radicals, etc.

2-

TOLUENE

In the toluene molecule, a hydrogen of benzene is
replaced by a methyl group (- CH3). Like benzene,

Toluene C7H8

toluene has very good solvent properties and a very

bp = 110.6°C

high octane number. Its toxicity, much less than that of

spgr = 0,871

and industrial solvents.

benzene, makes it preferable for uses in gasolines

As too much toluene is produced, most of it is processed to make benzene. Figure 2 provides the
main data for toluene.

3-

Cs AROMATICS: ETHYLBENZENE, XYLENES
a • Ethylbenzene

CH2 ~"~ CH3

Ethylbenzene C H
8

Ethylbenzene
10

b = 136.2°C
p

2

styrene.

1

spgr 5 = 0.871

00045_A_A

is

mostly

obtained

from

alkylation of benzene by ethylene and is
almost entirely dehydrogenated to make

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

3

b - Xylenes
The three xylenes or dimethyl benzenes are distinguished by the respective positions of the methyl
groups on the aromatic ring:

We see that the xylenes have very close volatilities, which makes their separation and purification
difficult. As shown in figure 3 for aromatics in Cs, only ortho and para xylene have important uses in
petrochemistry.

00045_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

4

II •

MAIN SOURCES OF AROMATIC HYDROCARBONS
World production of B.T.X. (Benzene - Toluene - Xylenes) comes mostly from:
-

catalytic reforming of gasoline

-

use of aromatics from pyrolysis gasolines
treatment of coal benzols

The current overall breakdown is shown in the table below.

Sources

% mass produced

Reformate

71

Pyrolysis gasoline

23

Coal benzols

6

Figure 4 indicates the world aromatic production capacity and production. It also indicates for each aromatic
the share of the sources mentioned.

1-

CATALYTIC REFORMING
This is currently the main source of BTX production in the world. This process, used by refiners to
improve the octane number of gasoline by production of aromatics, is also used in petrochemistry. It
produces a cut that is rich in aromatic hydrocarbons called reformate from which we can extract and
then separate aromatic hydrocarbons.
In practice, these units are most often located in refineries and are used, simultaneously or
alternatively, for refining or for petrochemistry.
a - Principle of the catalytic reforming process
The chemical transformations expected in catalytic reforming concern essentially the two families
of normal paraffins and naphthenes for which the feed is always relatively rich. The reactions used lead
to the following transformations:

n-paraffins
to C6-C10

naphthenes
to C6-C10

00045_A_A

Aromatics: benzene, toluene, xylenes and heavier
light paraffins
isoparaffins

Aromatics: benzene, toluene, xylenes and
heavier
light paraffins

© 2008 ENSPM Formation Industrie - IFP Training

5

They are carried out at high temperatures, on the order of 500°C, at low to average pressures
depending on the process and in the presence of a catalyst.
In these conditions, three types of chemical reactions are particularly important in this process:
aromatization, hydrocracking and coke formation reactions.
b - Catalytic reforming catalysts
Given the expected chemical reactions, catalytic reforming catalysts must have two types of activity:
-

the first must promote the structural changes to allow for ring formation from paraffins. This
function requires an acid catalyst

-

the second must facilitate dehydrogenations that lead to aromatics as well as
hydrogenations involved in hydrocracking. This hydro-dehydrogenating function is
provided by platinum, used alone or associated with other metals

This double function of catalytic reforming catalysts is obtained by using a porous alumina, the natural
acidity of which is enhanced by the addition of chlorine. The acid surface thus obtained is impregnated
with platinum, generally associated with other metals such as rhenium, germanium, tin, etc. The
quantity of chlorine used represents about 1 % by mass of catalyst and that of platinum 0.2 to 0.7% by
mass.
Catalytic reforming catalysts are thus highly elaborate and expensive products due to the use of
precious metals and the quantities of catalyst used in industrial units.
For a unit with 100 t/h of feed flowrate 45 to 70 tons of catalyst are needed depending on the process
used.
Also, catalytic reforming catalysts are highly sensitive to various poisons, which reduce their activity,
mostly:
-

coke, already mentioned
sulfur and nitrogen, which must first be eliminated from the feed

-

metals

c - Use of the process
• Pre-treatment
Given the requirements for the catalyst, the catalytic reforming feed must be freed of impurities: sulfur,
nitrogen, metals, etc. This is a hydrogen treatment to eliminate sulfur and nitrogen respectively in the
form of volatile hydrogen sulfide H2S and ammonia NH3 and to trap the metals.
• Catalytic reforming
We currently distinguish two types of facilities for:

-

conventional semi-regenerative catalytic reforming,

regenerative catalytic reforming,

conventional semi-regenerative catalytic reforming is characterized by regeneration of
the catalyst during periodic shutdowns. These processes cannot operate continuously at
high severities because the acceleration of coke formation would lead to excessively
frequent stops for regeneration

00045_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

6

An example of a process scheme for a semi-regenerative catalytic reforming unit is shown
in figure 5. This scheme is characterized chiefly by:
-

dilution of the feed by a gas rich in hydrogen drawn off in the separation section in
order to limit coke formation on the catalyst as much as possible

-

several stage furnace-reactors to bring the feed + gas rich in hydrogen mixture to
the reaction temperature and to compensate for the heat consumption of the
chemical reactions, which lead to uneven distribution of mass of catalyst in the
reactors
The temperature falls very rapidly in the first reactor in which the rapid endothermic
reactions occur. The quantity of catalyst here is thus limited to 10-15% of the total
mass. This phenomenon is a little less marked in the second reactor (about 20-30%
catalyst). The last reactor work at essentially constant temperatures given the
thermal compensation that exists between the slow endothermic reactions and the
exothermic reactions such as hydrocracking.

-

a separation section including:

a separating tank to obtain a gas rich in hydrogen, some of which is
recycled while the remainder constitutes the production of the unit
a stabilization column that separates the hydrocarbons into fuel gas,
LPG and stabilized reformate

-

a recycling compressor that sends the gas rich in hydrogen from the separating
drum to the line that carries the feed to the inlet to the unit

-

regenerative catalytic reforming is a change in the process to tolerate higher severities
based on the following guidelines:
-

functioning at lower pressure (about 15 bars) allowing for substantial
improvement of the reformate and hydrogen yields by promoting aromatization
reactions to the detrimental hydrocracking reactions. Coke formation is also strongly
promoted

-

improvement of catalysts to make them more stable, i.e. more resistant to
poisoning by coke and more selective to promote aromatization

-

modification of the process scheme with establishment of a system allowing for
continuous circulation and regeneration of the catalyst

These regenerative units, of which figure 6 (IFP regenerative catalytic reforming) provides
an example, allow for constant work at very high levels of aromatization while maintaining
good yields.
Also, the changes in the process in favor of lower pressures have an effect on the design of
the equipment. If we do not limit the resistance to the passage of the gases involved, the
energy consumed for the compression of the recycling gas becomes prohibitive at low
pressure
This led to major technological modifications for the furnaces, exchangers and reactors.
Figures 7 and 8 respectively present examples of equipment designed to limit pressure
drop:

00045_A_A

-

the feed-effluent exchanger is a plate exchanger (Packinox for example)

-

the reactor has a radial configuration

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

7

d - Products obtained
With conventional processes, the specific production of aromatics is facilitated by the reforming of
narrow cuts:
-

60-145°CforallBTX
65-85°C for benzene

-

85-110°C for toluene

-

110-145°C for xylenes

Regenerative technology is still better adapted to the production of aromatics. As it can withstand more
severe treatment conditions, it allows for intense cyclization of paraffins while maintaining good yields.
Depending on the type of process and the composition of the feed, the aromatic content of the
reformate may vary from 60 to 90% (mass).
The composition of the aromatic fraction of the reformate obtained by a regenerative process
processing a feed with distillation interval 107-160 is shown below:

% Weight
Benzene

2-4

Toluene

20-30

Ethylbenzene- Xylenes

35-50

Higher aromatics

20-35

e - Operating variables
The main variable used in the unit to obtain a reformate with a high degree of aromatization is the
reaction temperature, which can be adjusted with furnaces placed in front of each reactor.
Figure 9 shows the relationship between the aromatic content and the yields of the unit for two
feedstocks.
An increase in aromatic content is obtained on a given feed by increasing the reaction temperature,
which accelerates the chemical reactions and particularly hydrocracking reactions. This leads to:
-

a decrease of the reformate yield
greater production of gas

At the same temperature, a naphthenic rich feed that is more apt for reforming than a paraffinic rich
feed gives a reformate that is richer in aromatics. The same production of aromatics is thus obtained
with this type of feed at lower temperatures and provides a better yield of reformate and lower
production of gas.
There is a general rule for catalytic units related to the feed flowrate and thus the residence time of the
feed in the reactors: a reduction of the feed flowrate leads to a longer residence time, which prolongs
the chemical reactions and increases the degree of aromatization.
Pressure is not an operating variable in an existing unit, but it is however a determining parameter in
changes in the catalytic reforming process because new units work at low pressure.

00045_A_A

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8

f - Aging of catalyst - regeneration
In conventional units, the behavior of the catalyst is characterized by declining performance over
time, due essentially to progressive coke deposits on the surface. This loss of activity is compensated
by an increase in reaction temperatures, which promotes the production of gas and reduces the
reformate yield.
When the temperature becomes too high, the facility must be shut down and the catalyst regenerated.
This operation involves slowly burning the coke by introducing small quantities of oxygen into a current
of nitrogen circulated through the furnaces and reactors.
This catalyst thus recovers its surface and most of its properties after several complementary
treatments including, in particular, chlorination to compensate for the losses of chlorine that occur
during regeneration.
This addition of chlorine is also done during normal operation of the unit in the form of a small injection
of a chlorinated organic product. We thus compensate for the losses of chlorine, which is eliminated
from the surface of the catalyst with the reaction products.
The frequency of regeneration naturally depends on the unit's operating conditions. There is often one
regeneration every 6 months.
In regenerative units, the catalyst undergoes the same reconditioning steps within the regenerator to
recover its activity.

2-

STEAM CRACKING
After catalytic reforming, steam cracking is the number two source of BTX aromatic hydrocarbons in
the world. These aromatics, and especially benzene, are a substantial fraction of the C5-20O pyrolysis
gasoline cut.
The main feeds used for production of aromatics are naphthas and diesel fuels. In general, steam
cracking of diesel fuel produces less light constituents than treatment of naphtha and more heavy
products, which have a higher aromatic content. Thus the BTX concentration (mostly benzene) of the
C5-2OO cut increases when we switch from a naphtha feed to a diesel fuel feed. Also, depending on
the severity of the pyrolysis (characteristic related to the ethylene yield), the product yields differ.

00045_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

9

Feedstock

d

Naphtha

Diesel fuel

0.713

0.832

30-170

230-330

4
(°C)

Low

High

Low

High

C2H4 Ethylene

25.8

31.3

19.5

26.0

C3H6 Propylene

16.0

12.1

14.0

9.0

7.9

2.8

6.4

2.0

10.0

13.0

10.7

12.6

17.0

9.0

10.0

8.0

3.0

6.0

21.8

19.0

Severity

Yields (% weight)

C4H8 Butenes
BTX
C5-2OO gasoline (except BTX)
Fuel oil

3-

COKING PLANT BENZOLS
Aromatic hydrocarbons may come from coal rather than oil. During processing of coal into coke
needed for the production of pig iron, crude gases, benzols and tar are formed. After catalytic hydrorefining (elimination of sulfur, oxygen and nitrogen compounds), the benzols (80-160°C) give, by
distillation, a crude benzene cut containing the following hydrocarbons:

% Weight

Cyclopentane

2

Benzene

65

Toluene

18

Xylenes

6

Ethylbenzene

2

C

+

7

8

From this cut it is then possible to separate benzene and toluene.

00045_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

10

III -

THE MAIN PROCESSES FOR TURNING T.X. INTO B.T.X.
The production of aromatics is out of balance with market demand. For this reason, transformation processes
were developed to convert the least useful aromatics (toluene, metaxylene (mX)) to the aromatics that are
mostly easily used. The processes used aim above all to:
-

turn toluene into benzene

-

turn toluene into benzene and xylenes

-

turn toluene and Cg aromatics into xylenes

-

convert meta-xylene into ortho or para-xylene

The processes are:

1-

-

hydrodealkylation of toluene

-

disproportionation of toluene
transalkylation
isomerization of xylenes

HYDRODEALKYLATION OF TOLUENE INTO BENZENE
This pathway is used in particular when we want to make benzene from reformate.
The large share of toluene accompanying the benzene in the reformate is used to make toluene into
benzene. This reaction, done in the presence of hydrogen, corresponds to hydrodealkylation.
This process is also valuable for using toluene present in coking plant benzols.
The transformation principle is as follows:
C H

3

Toluene

Hydrogen

Benzene

Methane

°

Among the existing processes we distinguish those working:
-

thermally, the cracking of the methyl group (- CH3) is obtained at high temperature

-

with specific catalysts (alumina with 10-15% chromium oxide by mass)

This transformation can also apply to xylenes,
a - Characteristics of the chemical reaction
This chemical reaction is highly exothermic.
It consumes hydrogen. It is favored kinetically by higher temperatures. High pressure can be
favorable or unfavorable depending in the case. The operating pressure is thus a compromise.

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11

The main reaction is accompanied by side reactions, the most important of which are:
-

heavy aromatic formation (diphenyl, naphthalene)

-

coke formation

b - Operating conditions of a thermal process
The operating conditions generally involve operating temperatures on the order of 650 to 700°C and
require cooling of the reaction mixture by injection of cold products in the gaseous or liquid state. The
operating pressures are between 40 and 60 bars.
The pressure and the heat level require particular technologies for the reactor. It may be totally empty
or contain catalytic beds depending on whether the process used is purely thermal or uses a catalyst.
In both cases, the operating conditions for the hydrodealkylation remain basically the same because
the influence of the heat level reached is largely preponderant compared with the use of a catalyst.
c - Operating principle for a hydrodealkylation unit
Figure 10 shows a hydrodealkylation unit.
The feed mixed with hydrogen and the recycled product is put into the reactor, which is designed to
withstand high pressures, temperature rises and the corrosiveness of hot hydrogen.
Within the reactor, the quench is done with recycled gaseous hydrogen, which allows for limiting of the
temperature and the risks of product decomposition.
The effluent is then cooled down and sent to a high pressure separating drum in which the excess
hydrogen is separated and can then be recycled. The liquid product is stabilized using a column that
separates the light products from the heavy products, including the benzene and unprocessed toluene.
These two compounds are successively separated in two columns, with the untransformed toluene
being recycled.

Toluene

Benzene

Xylenes
in mixture

Among the existing catalytic processes, we distinguish those that catalyze the reaction:
-

in the liquid phase without hydrogen
in the gaseous phase in the presence or absence of hydrogen.

While hydrogen is normally useless for the reaction, it prevents coke formation, particularly for
processes in the vapor phase.
Several types of catalysts can be used, particularly zeolites.

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12

a - Operating conditions for a process in the vapor phase in the presence of hydrogen on a
zeolitic catalyst
The operating conditions for such a process are:
-

a temperature on the order of 400 to 500°C

-

pressure between 30 to 40 bars

-

a H2/HC molar ratio between 5 and 20

-

a H2 concentration in the recycling of at least 70%

b - Operating conditions for a process in the liquid phase without hydrogen on a zeolitic
catalyst
In this case, the operating conditions are:
-

temperature between 260 and 320°C
pressure between 40 and 50 bar

Compared to hydrodealkylation, dismutation of toluene has as its main advantages:
-

possible simultaneous production of benzene and xylenes
higher yield of aromatics

-

low or no consumption of hydrogen and thus lower investment and compression operating
cost

-

gentler operating conditions

But it also has the following drawbacks:
-

higher investment cost due to recirculation of a large quantity of untransformed toluene
a larger and more complex separation train.

TRANSALKYLATION
This reaction aims to make toluene in the presence of Co aromatic compounds into a mixture of
xylenes.
An example of the reaction is given below:

CH3

Toluene

CH3

CH3

Trimethylbenzenes

Xylenes

in mixture

in mixture

While this reaction can be carried out alone in a reactor called a transalkylator, it can also be done in
a dismutation reactor. In this case, introduction of C9 aromatics allows for control of the ratio of
benzene/xylenes formed. This makes the operation of a dismutation unit more flexible.
It follows from the above that the operating conditions used for the transalkylation reaction are very
close to those used in dismutation units.

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

13

ISOMERIZATION OF XYLENES
Of the three xylenes, metaxylene is of limited use for petrochemistry. It is a by-product from the
production of ortho and paraxylenes and can be used as a solvent or a base for a high octane
gasoline.
It is more and more frequently isomerized however. The purpose of the corresponding isomerization
units is to apply catalytic treatment to metaxylene to change the position of one of the two methyl
groups, yielding an ortho-meta-paraxylene

mixture that can then by retreated in the xylene

separation processes. This significantly increases the production of ortho and paraxylene.
If ethylbenzene and orthoxylene are not first separated, they are isomerized along with metaxylene.
The final isomerate is composed of a mixture of Cs aromatics.
The processes used are essentially catalytic processes in the vapor phase. Depending on the nature of
the catalyst, ethylbenzene, if present, is:
-

cracked or transformed by dismutation into a benzene C aromatic mixture. The catalysts
9

(alumina silica or promoted alumina) are used without hydrogen cover
-

isomerized to xylenes. Noble metal-based catalysts placed on silica-alumina or on chlorated
or fluorated alumina are used in the presence of hydrogen, which allows for isomerization of
ethylbenzene. The usual operating conditions are:

temperature between 350 and 480°C

pressure on the order of 10 to 15 bars

a H2/HC molar ratio of about 8-10.

The process shown in figure 11 uses a zeolitic catalytic system containing platinum.

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

14

IV -

MAIN SEPARATION PROCESSES USED TO OBTAIN AROMATICS
1 -

AROMATICS - NON AROMATICS SEPARATION
The separation of aromatics-non aromatics contained in a reformate or in a hydrogenated steam
cracker gasoline cut is done essentially by two processes: liquid-liquid extraction and extractive
distillation.
In some cases however, standard distillation is sufficient, particularly for obtaining toluene and a
mixture of xylenes to specifications when these are produced on effective reformers.
a - Liquid-liquid extraction
Liquid-liquid extraction processes are adapted to treatment of broad C6-Cs cuts. They are based on
the property of some polar compounds of selectively dissolving aromatic hydrocarbons and of being
not very miscible with paraffinic and naphthenic hydrocarbons.
The aromatic compounds dissolved in the solvent constitute the extract. The insoluble paraffinic and
naphthenic fractions in the solvent are called the raffinate.
The process is applied in an extraction column within which we circulate two liquid phases in counter
current, promoting their contact with trays or packing.
The main qualities required for liquid-liquid extraction solvents are the following:
-

high affinity for aromatics
non-miscibility with the feed to be processed

-

density clearly different from that of the feed to facilitate liquid-liquid decantation
ease of separation of extracted aromatics by standard distillation

The main solvents used are:
-

diethyleneglycol DEG (UOP process)
dimethylsulfoxyde DMSO (IFP process)

-

N-methyl pyrrolidone NMP (Lurgi-BASF process)
sulfolane (Shell process)

The operating principle of a liquid-liquid extraction unit is shown in figure 1 of figure 12.
The denser solvent is injected at the top of the liquid-liquid extraction tower and moves down in the
column, becoming richer in aromatics. The feed introduced at an intermediate level is shared between
a soluble part in the solvent and a low density insoluble part that moves up in the column. We generally
maintain a temperature difference between the top and the bottom of the column to improve the
selectivity of the operation.
The non-aromatic raffinate comes out at the top, and the aromatic extract and the solvent at the
bottom. A separation by standard distillation is then done to regenerate the solvent and to extract the
aromatic cut.
The table below indicates the standard compositions of the various flows obtained during a separation
by liquid-liquid extraction.
,
1

00045_A_A

Reformate composition

Feed % weight

Extract % weight

Refining % weight

Non aromatics

38

0.2

86.7

Benzene
Toluene

9.5
29.5

Xylenes + ethylbenzene
Heavy aromatics

25.5
7.3

19

45.5
26

4

2.8

6

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

15

b - Extractive distillation
Extractive distillation is a separation process adapted to cuts containing compounds of different
families with similar volatilities. When the expected aromatics correspond to one particular cut, it
becomes possible, after fractionating of the reformate, to apply this process. It is not suitable however
for treatment of the reformate, especially for a wide cut.
Industrially, we use extractive distillation to separate aromatics in C : xylenes, ethylbenzene, from
8

other hydrocarbons present in the reformates and to obtain benzene in the Ce steamcracker cut.
• Separation of aromatics in Cs
Part 2 of figure 12 shows an extraction facility for Cs aromatics. It includes:
-

prefractionating of the reformate to light reformate (containing benzene) and heavy
reformate

-

+

separation of the C cut by distillation, also yielding the C g and C7 cuts
8

treatment of the C

8

cut in an extractive distillation column using a solvent, for example

sulfolane, which is often used for this operation. The solvent that acts in the liquid phase
circulating in the column leads to a modification of the natural volatilities:

the aromatics held in the liquid phase become heavy and go out at the bottom of
the column

the non-aromatics have light behavior on the other hand and go out at the top of
the column

-

the solvent is then separated by distillation of the C

8

cut and returns to the top of the

extractive column
The C

8

cut obtained generally contains a small fraction of toluene. It typically has the following

composition:

% weight
Toluene

5

Ethylbenzene

20

Paraxylene

20

Metaxylene

35

Orthoxylene

20

• Obtaining benzene from a Ce cut
Figure 13 shows extractive distillation of benzene by NMP. The extractive distillation feed, if it is a C6
steam cracker cut after double hydrogenation, has the typical composition presented in the table
below. It contains only saturated hydrocarbons: paraffinics and naphthenics, referred to as "NonAromatics", and benzene, accompanied by traces of toluene.

00045_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

16

Family

Boiling point

% Weight

CO

(examples)

Cyclopentane (CP)

C5H10

N

49.3

3

n-hexane

C6H14

P

68.8

10

Methylcyclopentane (MCP)

C6H12

N

71.8

4

Benzene

C H

A

80.1

71

Cyclohexane

C6H12

N

80.7

4

11 dimethylcyclopentane

C7H14

N

87.8

1

n-heptane

C7H16

P

98.4

6.8

Methylcyclohexane (MCH)

C7H14

N

100.9

0.2

Toluene

C H

A

110.6

-

6

7

6

8

We can see that except for cyclohexane, the other hydrocarbons seem to be separable from benzene.
In practice, we see that due to the particular behavior of paraffin-aromatic or naphthene-aromatic
mixtures, n-hexane-benzene or methyl cyclohexane-benzene separations for example cannot be
efficiently done by standard distillation.
In the case of extractive distillation, the solvent used, pure NMP, has a particular affinity for benzene
and the more polarizable aromatics. In these conditions, the saturated paraffinic and naphthenic
hydrocarbons will all become "light" with respect to benzene, the heaviest of the "lights" being
methylcyclohexane (MCH).

00045_A_A

Natural scale

Scale of volatilities

of volatilities

in the presence of solvent

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

17

In the extractive column the feed rich in benzene is put in at an intermediate level. The solvent,
injected several trays under the top of the tower to avoid losses of solvent in the non-aromatic raffinate,
is enriched in benzene as it moves down from tray to tray. The Non-Aromatics become concentrated in
the vapor phase and are extracted at the top of the column. At the bottom of the column, after
reboiiing, we obtain the NMP-Benzene mixture, which is directed to the solvent regeneration tower
that separates the benzene (99.95% purity) from the solvent, which is recycled to the extractive
column.
The two towers work in a vacuum to lower the distillation temperatures and for better efficiency of the
solvent in its capacity to modify the volatility differences.
Lower temperatures also limit phenomena of thermal degradation of the solvent molecules.
We see that while it is valuable to lower the distillation temperatures, these should not be too low,
because this could lead to liquid-liquid segregation phenomena, making the solvent inoperative.

2-

SEPARATION OF AN AROMATIC FROM OTHER AROMATICS
a - Separation of benzene
The separation of benzene is problematic when it is with non-aromatic hydrocarbons as in the case of
the C6 steamcracker cut. But when we obtain a BTX cut, from a reformate after extraction for example,
the separation of benzene is done by standard distillation and does not present any particular
problems.
Benzene has a boiling point of 80.1 °C, relatively far from that of toluene (110°C) and separation is
consequently not too difficult, even when a high level of purity for benzene is expected.
b - Separation of toluene
To increase benzene production, toluene can be treated in a hydrodealkylation, transalkylation or
dismutation installation.

c - Separation of a mixture of aromatics in Cs
Given the small volatility differences between the various Cs aromatics, the boiling points of which are
given below, distillation separations are difficult or even impossible.

Normal boiling point (°C)
^

00045_A_A

Ethylbenzene

136.2^

Paraxylene

138.4

Metaxylene

139.1

Orthoxylene

144.4

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

U.0O

18

The practical consequences are the following:
-

ethylbenzene can only be separated from xylenes with a superfractionating installation.
This is available from Union Carbide and has 400 trays divided into two columns of 200
trays and consumes a great deal of energy. It yields 99.8% ethylbenzene with a rate of
recovery of 95.4%

-

meta and para xylene cannot be separated by standard distillation because they have
almost identical volatilities. Extractive distillation is also inoperative in this case because
the solvents used can only distinguish the constituents as a function of their chemical family

-

orthoxylene can be separated from other Cs aromatics by standard distillation. The
separation is difficult however and requires a superfractionating column with between 100
and 180 trays. Figure 14 shows the separation scheme for C

8

aromatics. Orthoxylene is

obtained at the bottom, the ethylbenzene, metaxylene and paraxylene mixture comes out at
the top and is steered to the paraxylene separation unit on a molecular sieve
d - Separation of paraxylene by adsorption
The process by crystallization used until 1970 was costly (refrigeration chain, filtrations, spin drying,
etc.) and the recovery of paraxylene was not very efficient even though the purity obtained was very
high.
Separation processes on molecular sieves (PAREX of U.O.P. and ELUXYL of IFP) are based on the
adsorbability difference of xylenes on a particular porous, solid support (special zeolite),
paraxylene being much more strongly adsorbed than the other xylenes and ethylbenzene.
Practically speaking, we can do this operation with a fixed adsorbent bed. A limited quantity of xylene
mixture (A + B) is injected at the top of the adsorbent bed and the mixture is "pushed" through the
column by a desorbent D. The two substances A and B progressively separate in the column. We
collect successively as output compound B (the least strongly adsorbed) and then compound A (the
most adsorbed), which must then be separated by distillation of solvent D, which is recycled to the
column. The figure below shows the concentration profiles in the column for two successive situations.
A : Paraxylene
B : Other xylenes
D : Toluene
Feed

Desorbent

A+B

D

Composition of liquid, %
0)

100

Fixed bed

Raffinate

Extract

B+D

A+D

Discontinuous adsorption on fixed bed

00045_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

CL

19

This process does not allow for continuous operation and requires the use of very large quantities of
adsorbent.
For continuous operation and to limit the mass of adsorbent used, the feed and the adsorption solid
must circulate in counter current in a column. Such a process is shown in the diagram below.
A : Paraxylene
B : Other xylenes
D : Toluene

Raffinate
B+D

Feed
A+B
Extract
A+D

Desorbent

Continuous adsorption in counter-current
With this technique and by varying the solid and liquid flows, we can keep the concentration profiles
in the column stationary. The feed and desorbent injection points and the draw off points are found at
clearly determined positions of the column. The counter current "moves back" constituent A, which is
the most adsorbed, with the poorly adsorbed constituent B " a d v a n c i n g " in a sense with respect to the
injection point of the feed.
Such a technique is unfortunately impossible to apply because it is materially very difficult to have the
solid adsorbent bed circulate in a homogeneous fashion.
The approach used involves simulating the counter-current by leaving the adsorption solid in the
fixed bed. Instead of circulating the solid in the column, we modify at regular intervals the levels of
the injections and drawings to follow the concentration peaks that move over time. In practice, a
rotating distributor or any other calculator-controlled system handles the coordination of the injections
and drawings arranged upstream and downstream from the various adsorbent beds placed in the
column.
These processes allow us to recover more than 90% of the paraxylene from the feed with a very high
purity - greater than 99%.
The simplified scheme of a PAREX installation is shown in figure 15 and that of an ELUXYL
installation, in figure 16.

00045_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

20

V-

STANDARD SCHEMES FOR SEPARATION AND PURIFICATION OF AROMATICS
1 -

TREATMENT OF REFORMATES
The treatments used for reformates can be relatively complex. If the reformate is made of a general
BTX cut, it can be fractionated to make a benzene-toluene cut and a xylene cut for which we use
specific treatments in each case. The diagram below is for a comprehensive extraction treatment to
obtain benzene, orthoxylene, paraxylene and which has a unit for hydrodealkylation of toluene and a
unit for isomerization of xylenes. Figure 17 shows an aromatic complex different from that described
below.

CATALYTIC
REFORMING

Reformate

EXTRACTION
OF AROMATICS

Non
aromatics

Liquid-liquid extraction
Extractive distillation

_:Coup§ BTX
SEPARATION
BY
DISTILLATION

HYDRODEALKYLATION

Toluene-Xylenes-Ethylbenzene

,0 0

SEPARATION
BY
DISTILLATION

9

Xylenes-Ethylbenzene

o
m

Xylenes

SEPARATION OF
XYLENES
BY DISTILLATION

P

Meta and paraxylenes-Ethylbenzene

SEPARATION ON
MOLECULAR
SIEVE

ISOMERIZATION
OF XYLENES

^'/iijia,;!!:;)

y

Metaxylene
Ethylbenzene
- •

00045_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

Metaxylene
Ethylbenzene

21

TREATMENT OF STEAM CRACKING GASOLINES
The diagram below summarizes the succession of treatments applied to pyrolysis gasolines for the
production of benzene and aromatics.

Extraction
of aromatics
Naphtha
or diesel fuel

Steam cracking

Fractionating
by standard
distillation

Hydrogenation
of gasolines,
1st and 2nd steps

Extractive
distillation
(benzene)
Liquid-liquid
extraction
(BTX)

BENZENE
Toluene
Xylenes

After hydrostabilization of the pyrolysis gasoline that involves making diolefins into olefins ( 1

st

hydrogenation step), we can isolate the C6 cut that is very rich in benzene by distillation. An example
of the composition of this cut is presented in the table below:

Benzene

82.4 % mass

Non Aromatics

17.6% mass

MAV mg/g

<2

Bromine index g/100 g

27

Total sulfur

215 ppm mass

Application of the separation process using a solvent requires a new hydrogenation or new hydrotreatment. This section, called the 2

n d

hydrogenation step, must totally eliminate the olefins and

sulfur present in order to ensure that the specifications for the purity of the benzene are met.
These two reactions are carried out at a temperature close to 300°C on catalysts made from nickelmolybdenum sulfides (hydrogenation of olefins) and cobalt-molybdenum sulfides (hydrodesulfuration,
HDS).
The usual performances of this hydrogenation yield, without loss of benzene:

00045_A_A

-

olefin content practically zero: I Br less than or equal to 2 mg/100 g

-

total sulfur content less than 1 ppm mass
thiophenic sulfur content less than 1 ppm mass

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

22

3-

TREATMENT OF BJNZOLS
Coking plant benzols are composed of hydrocarbons with boiling points in the 50-200°C interval. Not
including impurities, the typical composition indicated below shows the high aromatic content of this
type of product.

% Weight

Benzene

70

Toluene

20

Xylenes

7

Other

3

Before separation of the aromatics, we do a hydro-desulfuration treatment to eliminate the sulfur,
nitrogen, oxygen and chlorine contained in the crude benzols and to saturate the olefins and diolefins.
The general benzol treatment diagram is as follows:

•(

Crude

Fractionating
Hydrotreatment

benzols

by standard

Hydrodealkylation

distillation

Toluene - Xylenes

00045_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

BENZENE

enspm
IFP

Refining-Pelrochemicals-Chemicals-Engineering

TRAINING

NATURE OF AROMATIC HYDROCARBONS.
SOURCES AND ASSOCIATED PROCESSES

— Figures —

BENZENE

Figure 1

TOLUENE

Figure 2

C AROMATICS

Figure 3

DOMESTIC AND WORLDWIDE AROMATICS PRODUCTION

Figure 4

CATALYTIC REFORMING - Semi-regenerative unit

Figure 5

CATALYTIC REFORMING - IFP regenerative process

Figure 6

COMBINED FEED HEAT EXCHANGER - Packinox

Figure 7

CATALYTIC REFORMING RADIAL REACTOR

Figure 8

INFLUENCE OF SEVERITY ON CATALYTIC REFORMING UNIT YIELD

Figure 9

8

TOLUENE HYDRODEALKYLATION

Figure 10

ISOMERIZATION

Figure 11

AROMATICS AND NON-AROMATICS SEPARATION P R O C E S S E S

Figure 12

EXTRACTIVE DISTILLATION OF BENZENE - Use of NMP

Figure 13

XYLENES SEPARATION

Figure 14

PARAXYLENE SEPARATION ADSORPTION - PAREX P R O C E S S

Figure 15

PARAXYLENE SEPARATION BY ADSORPTION - ELUXYL P R O C E S S

Figure 16

PARAXYLENE PRODUCTION UNIT

Figure 17

05/06/2008

enspm

BENZENE: Origin • Production - End uses

FORMATION INDUSTRIE
IFP

a

• Figure 1 —

TRAINING

End uses
PRODUCTION CAPACITIES

39 Mt/y

MAIN END U S E S F O R B E N Z E N E

% WORLD
Production of styrene

World

STYRENE
PRODUCTION
29.7 Mt/y

50%

co

World

6.9 Mt/y

Western Europe

0.9 Mt/y

France

Benzene
C H
6

6

Ethylene
C H
2

Ethylbenzene

Styrene

Hydrogen

C8H-10

C H

H

4

8

8

2

MAIN PRODUCTION UNITS
Production of phenol and acetone
COMPOSITION
38%

ALKYLATION

PHENOL-ACETONE

CO

20%
Benzene

Propylene

Cumene

C H

C3H6

C9H12

6

6

Oxygen
0

Production of cyclohexane

Toluenedealkylation—K
v^^ransalkylaft^

00
00

CYCLOHEXANE
20°'-

15%

CO
Benzene
C H
6

6

Hydrogen
3H

2

© 2008 ENSPM Formation Industrie - IFP Training

Cyclohexane
C H12
6

Phenol

Acetone

C H OH

CH3CO CH3

6

2

5

enspm
FORMATION INDUSTRIE
IFP

I

TOLUENE: Origin • Production - End uses

TRAINING

End uses

• Figure 2 •

MAIN END U S E S F O R T O L U E N E

% WORLD
PRODUCTION CAPACITIES
Production of benzene
21 Mt/y

World

PRODUCTION

BENZENE

14 Mt/y

World

1.9 Mt/y

Western Europe

60kt/y

HYDRODEALKYLATION
+

40%

OO

France

MAIN PRODUCTION UNITS

Toluene

Hydrogene

C H

H

7

8

Benzene
C H

2

6

Methane
CH

6

Benzene and xylene production

BENZENE-XYLENES

DISPROPORTION

16%
v. : p s | f i n :
WPIHIII"!

77%
Toluene

Toluene

J

V
Y
2C H
7

Cfml. jftiT^

N.

8

mm
© 2008 ENSPM Formation Industrie - IFP Training

Xylenes
Benzene
C H
6

6

(ortho. meta. para)
C H1
8

0

4

Cs AROMATICS; Origin - Production • End uses

FORMATION INDUSTRIE
IFP

TRAINING

PRODUCTION CAPACITIES
3
12

Mt/y
Mt/y

OX World
dePX

End uses

MAIN END U S E S

• ETHYLBENZENE

% WORLD

• Figure 3-

Production of styrene

PRODUCTION

DEHYDROGENATION
2.2
9
20

Mt/y
Mt/y
Mt/y

OX
PX
EBz

co
STYRENE
Ethylbenzene

99%

C H
8

MAIN PRODUCTION UNITS

Styrene

Hydrogen

C H

H

1 0

8

8

2

• XYLENES
Production of phtalic anhydride from ortho-xylene
<*f&m*%

I

I

OXIDATION

^

*

CO

Orthoxylene

Oxygen

C Hio

3 0

8


Phtalic anhydride
C H 0
8

2

4

3

Water
3H 0
2

Production of terephtalic acid (T.P.A) and dimethylterephtalate (DMT) from paraxylene

CP*
r

OO
OO

V

0 0

Paraxylene

Oxygen
3 0

OXIDATION

Terephtalic acid
C H 0

Water
2H 0

Dimethylterephtalate

Water
4H 0

8

2

6

2

4

' **
ESTERIFICATION
Paraxylene
C H
8

1 0

Methanol
2 CH 0H
3

© 2008 ENSPM Formation Industrie - IFP Training

C

H

10 10°4

2

enspm

— Figure 4 —

FORMATION INDUSTRIE
IFP

T R A I N I N G

DOMESTIC & WORLDWIDE AROMATICS PRODUCTION

World

World

capacity

production

Mt/y

Mt/y

1999

1999

Benzene
Toluene
Blended
Xylenes

39
21
31

30
14,5
23.5

Total

91

68

Ori gin

Reforming

32%
77%
85%

Steam-

Coal

cracking

38%
17%
9%

Miscellaneous

10%
6%

20%

1%

5%

These data highlight that steamcracking is the main way to produce benzene and reforming the main way to
produce xylenes.
Several sites in France are concerned by aromatic production. The table hereunder shows their nature and
the location of plants as well as main feedstocks used.

Company location

Main productions

Feedstocks

TOTAL France - Feyzin

B-T-X

Pyrolysis gasoline

ATOFINA - Gonfreville

Benzene

Pyrolysis gasoline

TOTAL France- Gonfreville

B-T-X

Reformate
Isomerization
of xylenes

ATOFINA - BP

Benzene

Pyrolysis gasoline

Benzene

Pyrolysis gasoline
Coal

Lavera
ATOFINA - Carting

Hydrodealkylation
of toluene
SHELL C H I M E

Benzene

Pyrolysis gasoline

Benzene

Reformate

Berre
TOTAL France
Lacq

I

Hydrodealkylation
of toluene

00046 A A

--

© 2008 ENSPM Formation Industrie - IFP Training

enspm
IFP

— Figure 5 —

CATALYTIC REFORMING
Semi-regenerative Unit
— Simplified flow scheme —

FORMATION INDUSTRIE
TRAINING

REACTION SECTION
FURNACES and REACTORS

F

SEPARATION SECTION

RECYCLING
COMPRESSION
SECTION

\

/ - r — \ including
/
2 t/h of
pure hydrogen
a

<_L>
STABILIZATION
COLUMN

40

<flO

Temperature (°C) ( ^ )
© 2008 ENSPM Formation Industrie - IFP Training

Pressure (bar abs)

<^

^> Flowrate (t/h)

ay

enspm
FORMATION INDUSTRIE
IFP

TRAINING

ELUTRIATOR
• Operating pressure

4-5
bar abs.

H
• -j^(mol/mol)
2

• Catalyst
•Catalyst cycle

• Figure 6 —

CATALYTIC REFORMING
IFP regenerative process
- Simplified flow scheme -

REGENERATOR

3
45 - 601
1001 of feed

H rich
'gasrecycle2

2-3 days

^^^j^lSt

loop

Hydrogen
for reduction

JUTe.Recyle
loop
z
O
i—
<
cc
<
Q.

Furnace

FEEDSTOCK
60-145 °C
F1
Lift gas
© 2 0 0 8 ENSPM Formation Industrie - IFP Training

Lift gas

Lift gas

enspm
FORMATION INDUSTRIE
IFP

n

TRAINING

COMBINED FEED HEAT EXCHANGER
— Packinox —

Effluent from

Feed to
first furnace

ast reactor

Vent

Hot bellows

Manhole

Effluent header

FEED/EFFLUENT
Bundle support

EXCHANGER
(Packinox)

Pressure vessel

Welded plate bundle

Brackets (or skirt)

Effluent header
Venturi
Cold bellows

Spray bar

Liquid feed

Effluent

Recycle gas

Drain

© 2008 ENSPM Formation Industrie - IFP Training

• Figure 7 —

enspm
FORMATION INDUSTRIE
IFP •
TRAINING

CATALYTIC REFORMING RADIAL REACTOR

• Figure 8 •

Carbon steel

Diffuser

Shield
Refractory
cement

Stainless
steel

Ceramic

Catalyst

Central
tube
Scallops

Metallic
wire

Ceramic

© 2008 ENSPM Formation Industrie - IFP Training

enspm
FORMATION INDUSTRIE

INFLUENCE OF SEVERITY
ON CATALYTIC REFORMING UNIT YIELD

— Figure 9 —
-

FEEDSTOCK: Naphtenic Naphtha (86 - 165°C ASTM)

-

FEEDSTOCK: Paraffinic Naphtha (86 -165°C ASTM)

enspm
FORMATION INDUSTRIE
IFP

TOLUENE HYDRODEALKYLATION
— Simplified scheme —

TRAINING

— Figure 10 —
Temperature (°C)

Pressure (bar abs)
H2 recycle loop
II ^lill
680

Light ends

40

Toluene

FURNACE

Quench
DISTILLATION

fyhx&r

COLUMNS

m . J . . . . . t . . . . » ,

730

Non converted toluene recycle loop

VZZ)

1

Heavy ends
© 2008 ENSPM Formation Industrie - IFP Training

enspm
FORMATION INDUSTRIE
IFP

TRAINING

ISOMERIZATION
Simplified scheme —

© 2008 ENSPM Formation Industrie - IFP Training

— Figure 11 —

enspm
FORMATION INDUSTRIE
IFP

TRAINING

AROMATICS AND NON-AROMATICS SEPARATION PROCESSES
Figure 12 —

fig 1. Liquid-liquid extraction
Raffinate
non aromatics
Lean solvent

SOLVENT
REGENERATION
AR- NonAR

JIMMmmm

C6-C8

Benzene
Toluene
Xylenes

Extract
solvent + aromatics

fig 2. Reformate prefractionation and extractive distillation of the Cg cut
LIGHT REFORMATE C

I

5

Non aromatics
^ raffinate

TOL-NonAR

SOLVENT
REGENERATION

mm

Heavy reformate

4

Solvent
+

C AROMATICS

C aromatics

EB, PX, MX, OX

+

C CUT

8

9

8

Standard distillation columns

Extractive distillation columns

© 2008 ENSPM Formation Industrie - IFP Training

enspm
FORMATION INDUSTRIE
IFP

TRAINING

EXTRACTIVE DISTILLATION OF BENZENE
Use of NMP
— Operating conditions —

EXTRACTIVE

SOLVENT

COLUMN
75

— Figure 13-

REGENERATOR

h r
- > To vacuum system

Solvent

• > To vacuum system

0.5,
C 1 C >

,

*

12

o

n

Solvent + benzene

Temperature (°C)
175
Pressure (bar abs)

30'
Solvent recycling
M

© 2008 ENSPM Formation Industrie - IFP Training

r> n « -

'' <

>

Flow rate (t/h)

enspm
FORMATION INDUSTRIE
IFP

— Figure 14-

TRAINING

XYLENES SEPARATION

Temperature (°C)

( ^ )

Pressure (bar abs)
Toluene

CH -CH3
2

198

170
Ethylbenzene
tbp = 136.2X

5

<

CH

3

Metaxylene
tbp = 139.1X
MOLECULAR
SIEVE
DISTILLATION

ADSORPTION

COLUMN

UNIT

9 -

Paraxylene

SUPERFRACTIONATOR
EB, pX and mX

tbp = 138.4X

215
CH

3

Orthoxylene
tbp = 144.4°C
CH

© 2008 ENSPM Formation Industrie - IFP Training

3

J

enspm
FORMATION INDUSTRIE
IFP

TRAINING

PARAXYLENE SEPARATION ADSORPTION
PAREX PROCESS
— Simplified scheme —

•Figure 15-

Desorbent recycle loop (Toluene)

Desorbent
separation
column

Tonb 6

Raffinate

Tonb 1
Desorbent
separation
column

V : rotative valve

© 2008 ENSPM Formation Industrie - IFP Training

PARAXYLENE SEPARATION BY ADSORPTION
ELUXYL PROCESS
— Simplified scheme —
— Figure 16 —

© 2008 ENSPM Formation Industrie - IFP Training

enspm
FORMATION INDUSTRIE
IFP

— Figure 17-

PARAXYLENE PRODUCTION UNIT

TRAINING

TOL
H
Heavy aromatics Cg ARO
column

^Miliar

2

Stabilizer

J ,

C - Cg ARO

> Detoluenizer

8

Transalkylation
unit

Adsorber

TOL + TMB •»•* 2XYL
C jARO

TOL-C -CgARO

1f

8

TOL

Cg ARO

Adsorber

Stabilizer
i

Benzene Toluene
column column

TOLUENE
; + ox + PX
2 TOL

BZ + XYL
•c

TOL -C -Cg ARO

BZ-TOL-C -Cg ARO

8

8

C - C g ARO (+TOL)

+
9

ARO

BZ

: Benzene

TOL

: Toluene

XYL

: Xylenes mixture

MX

: Metaxylene

OX

: Orthoxylene

PX

: Paraxylene

EB

: Ethylbenzene

8

ilTlfV

L
TOL-C ARO (EB + XYL)
8

Heavy
aromatics
separation

Paraxylene
adsorption
unit

TOL + PX

TMB : Trimethylbenzene

w

EB + MX + OX

Reformate + EB + MX + OX

Cg ARO

MX + OX + EB
4-

Desorbent

MX + OX + PX

•K

(

'T~("T

© 2008 ENSPM Formation Industrie - IFP Training

.'1

^L-Jsri

Refining-Petrochemicals-Chemicals-Engheering

|

FORMATION I N L i U J i n F
ITP

T R A I N I N G

STYRENE MONOMER PRODUCTION

I

-

II -

CHARACTERISTICS AND MAIN U S E S OF S T Y R E N E

1

1 -

Characteristics of styrene

1

2

Economic environment and main uses

1

-

MAIN S O U R C E S OF STYRENE

4

1 -

Production of ethylbenzene from benzene and ethylene

5

2

Dehydrogenation of ethylbenzene into styrene

9

-

PC ARO - 00048.A. A - Rev. 2

© 2008 ENSPM Formation Industrie - IFP Training

05/06/2008

I

1

CHARACTERISTICS AND MAIN USES OF STYRENE
1-

CHARACTERISTICS OF STYRENE
Styrene is a compound that includes a benzene ring to which a vinyl group is attached (vinyl radical:
- C H = CH ).
2

Its range of inflammability in air is from 1 up to 6%.
Styrene production is mostly for the production of numerous polymers. Its tendency to polymerize
easily means that it must be inhibited to prevent accidental reactions. The most commonly used
inhibitor is PTBC (paratertiobutylcatechol). Its reactivity is due to the double bond of the vinyl group,
which allows for association of a large number of molecules.

2 -

ECONOMIC ENVIRONMENT AND MAIN U S E S
Styrene accounts for approximately 50% of the consumption of b e n z e n ^ which itself accounts for
about 66% of the world market for aromatics. The world market for aromatics, in terms of weight, is
close to 60 to 65% of the world market for ethylene.
In other words, the styrene market represents about 33% of the market for aromatics.
The main uses of styrene are for commonly-used thermoplastics. In round figures, this represents:
-

50% for compact polystyrene (crystal or standard and high-impact) and expansible

-

polystyrene
15% for SBR rubber (Styrene Butadiene Rubber)

-

11 % for ABS copolymers (Acrylonitrile - Butadiene - Styrene)

y-VsT^

a - Standard polystyrene
If the associated molecules are only styrene molecules, we obtain polymeric chains of polystyrene.

"~~ C H o — CH ~~~ CHo — CH - ~ C H o — CH —

The product obtained is hard and breakable. We call it crystal polystyrene.

00048_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

2

b - High-impact polystyrene
If polymerization of styrene is done in the presence of polybutadiene, this yields high-impact
polystyrene. The polymer acquires resistance to shocks that crystal polystyrene does not have.

Polybutadiene chain

Chains of polystyrene

This is a two-phase graft polymer. The polystyrene chains generated on those of polybutadiene allow
for anchoring of the rubber phase within a plastic matrix that is produced simultaneously and
composed of only polystyrene chains. In practice, the polybutadiene is first dissolved in the styrene.

c - Other polymers
• PSE
When we produce polystyrene that includes an inflating agent, we generate expansible polystyrene.
After expansion this becomes expanded polystyrene.
• SBR
If the reactivity acts not with other styrene molecules but rather with one or several other types of
molecules, we produce copolymers. We thus obtain styrene-butadiene rubber (SBR) by
copolymerizing styrene and butadiene according to the following diagram in proportions of close to
25% styrene:

"~" C H 2 "

- -

CH ~~" CH2 — CH — CH — CH2

Association of a styrene base unit
and a butadiene base unit

The reaction produces a so-called statistical polymer. We see a double bond within the butadiene base
unit that can be used later to vulcanize rubber, for example.

00048_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

3

• ABS
Copolymerization of styrene and acrylonitrile in the presence of chains of previously produced
polybutadiene forms A.B.S. resins (Acrylonitrile - Butadiene - Styrene).

Chain of polybutadiene

Butadiene

Butadiene

CD
c:
CD

CD
cr
CD

>.

co

Butadiene

co

I
CD
d

CD

lo

CD
c:
CD

&
CO

co

_o
&•

o

<

This graft polymer is from this polymerization of a styrene-acrylonitrile mixture of which some of the
chains produced graft on to the polybutadiene that was first dissolved in the styrene-acrylonitrile
mixture.

00048_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

4

II •

MAIN SOURCES OF STYRENE
The diagram below shows the different routes for styrene production.

Most styrene is obtained by dehydrogenation of ethylbenzene. This latter compound can also be used to
produce propylene oxide, which is used for simultaneous production of styrene.
Directly or indirectly, all styrene is produced from ethylbenzene.
This intermediary is about 95% produced from benzene and ethylene by a chemical reaction called
alkylation.
Ethylbenzene is also present in the Cs reformate and can be separated by distillation in a superfractionating
unit.
Regardless of the means used to obtain ethylbenzene, 99% of its production is for making styrene.

00048_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

5

1 -

PRODUCTION O F E T H Y L B E N Z E N E FROM B E N Z E N E AND E T H Y L E N E
This is currently the most frequent approach for obtaining ethylbenzene.
a - Reaction involved and characteristics
The chemical reaction implemented is an alkylation reaction that involves attaching an alkyl group
(ethyl radical: - CH2 - CH3) to an aromatic molecule (benzene) using an olefin (ethylene).

CH = CH
2

Benzene

2

Ethylbenzene

Ethylene

This reaction is highly exothermic. The heat produced is eliminated by:
-

vaporization of part of the reaction medium if it is in the liquid phase

-

refrigeration of the reaction mixture by heat exchange
or control of the temperature by injection of cold benzene and ethylene

Lower temperatures and higher pressures promote alkylation reactions. These require the presence
of a catalyst system to accelerate the chemical transformation.
The choice of the type of catalyst used is the most important distinguishing criterion for classifying the
various processes used.
b - Main processes: catalysts and operating conditions
The catalysts used in the production of ethylbenzene all have acidic characteristics.
We distinguish processes for which the catalytic systems are:

00048_A_A

-

Lewis acids such as aluminum trichloride

-

ZSM5 type molecular sieves for example

(AICI3) or b o r o n

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

trifluoride

(BF3)

6

Each catalyst is integrated with a particular process. While liquid phase units working with aluminum
trichloride are still the most common, we see that liquid or vapor phase units using molecular sieves
are the way of the future. With these, there is no need to worry about eliminating the aqueous solutions
of catalytic residues. As for the process that uses boron trifluoride, it is ruled out due to the dangers
involved in handling this compound.
c - Problems of side reactions
The chemical reaction that is expected is not the only one that occurs. There are side chemical
reactions, chiefly continuation of the alkylation reaction on the ethylbenzene formed, leading to
heavier polyalkylates.
To limit the yield of these by-products, we feed a quantity of benzene greater than that needed for the
reaction into the reactor. This increases the probability of a meeting between benzene and ethylene
molecules to form ethylbenzene. The ethylbenzene formed is diluted by the excess benzene and thus
has little chance of meeting a new ethylene molecule.
This is not sufficient to totally eliminate by-products however. We generate polyalkylates, which are
recycled after being isolated in some cases.
Polyalkylates can react with benzene to form an additional quantity of ethylbenzene by a
transalkylation reaction. This reaction is slower that the alkylation reaction and is limited by a
chemical equilibrium. It is also athermic.
One of the possible reactions can involve benzene and paradiethylbenzene molecules.

C H
2

5

C H

5

2

C H
2

Diethylbenzene

Benzene

5

Ethylbenzene

In general, the recycling is done in the alkylation reactor, but in some cases it can be used to feed a
separate reactor called a transalkylator in which we do only the polyalkylate transformation.
Regardless of the option chosen, this increases the yield of ethylbenzene.

00048_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

7

d • Operating goals
These are:
-

search for maximal "ethylene selectivity". This is expressed as the share of ethylene of
the feed finally used in the form of ethylbenzene.
The "ethylene selectivity" is given by:
, ..
Ethylene used in ethylbenzene
Ethylene selectivity =
Feed ethylene

J

1

0

n
0

n
=

7

3

%

In practice, this criterion is obtained from analysis of the reactor effluent.
Its value, close to 65-75%, corresponds to the yield of ethylbenzene with respect to the
ethylene put in initially, assuming that all of the ethylene has reacted.
-

maintaining an excess of benzene that is monitored by calculating the ratio of the number
of moles of benzenic ring present in the reactor effluent to the total number of moles of
ethylene used.
The benzene/ethylene molar ratio is generally kept between 2 and 2.5 in liquid phase units
using aluminum trichloride.
In units that use molecular sieves, these can reach values on the order of 4-6 to limit the
temperature level and to maintain catalytic activity.

e - Example of alkylation unit: alkylation process in liquid phase using aluminum chloride as a
catalyst
A diagram of the unit is shown in appendix n°1. The process includes four main sections:
-

a section for drying the benzene feed because water is a poison for the catalyst used. We
aim for a water content of less than 30 ppm

-

a reaction section in which the dry benzene, ethylene, and the aluminum chloride (AICI3)
based catalytic complex and its ethyl chloride C2H5CI promoter come into contact. This is
done in the alkylation reactor, which has an internal surfacing that can withstand an acidic
attack, because HCI can form due to the nature of the catalyst

-

a treatment section where, initially, the catalytic complex is separated from the alkylate by
decantation and then recycled to the reactor. The alkylate is not free of catalyst. The
catalyst is destroyed by water, soda and ammonia washings. The ethylbenzene produced
must be separated from chlorine compounds in order to meet the specifications required for
the next step of styrene production.

-

a distillation section to separate the various components of the crude alkylate with the
catalyst removed
The first column gives at the top benzene that did not react and which is recycled at the
drying section. The bottom product feeds a second column used to separate the
ethylbenzene from the heaviest products. These are separated in a final column, with
polyalkylates coming out at the top for recycling. The residue is used as fuel.

00048_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

8

The table below shows the specifications required for benzene and ethylene feeds in this type of unit.

Benzene

Ethylene

Non aromatic

300 ppm maxi

Acetylene

2 ppm maxi

Toluene

150 ppm maxi

Ethane

600 ppm maxi

Methane

300 ppm maxi

Propane

10 ppm maxi

CO2

5 ppm maxi

No sulfur
I
Water content < 30 ppm
(drying necessary)

J

reaction
poisons

The average composition of effluents in the alkylator is as follows on average:

Compounds

% Mass effluent

Ethylbenzene

45

Polyethylbenzene

15

Benzene

39

Heavy

<1

Despite the dilution by the benzene we see that there is a large share of PEB (polyethylbenzene).
The fractionating done on the reaction effluent yields ethylbenzene with the following typical
specifications:

Compounds
Ethylbenzene

99.6% mass mini

Benzene

400 ppm maxi

Diethylbenzene

20 ppm maxi

Toluene

00048AA

Values specified

2500 ppm maxi

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

9

D E H Y D R O G E N A T I O N O F E T H Y L B E N Z E N E T O MAKE S T Y R E N E
Obtaining styrene from ethylbenzene alone requires a dehydrogenation treatment in order to give the
reactive double bond used in polymerization in particular.
a - Chemical reaction involved - Operating conditions
The expected reaction is written:
CH

2

— CH

CH =

3

CH

+

Ethylbenzene

Styrene

2

H

2

Hydrogen

S

It has the following characteristics:
-

strong endothermicity, i.e. the reaction absorbs a lot of heat. The calories needed for it
are mostly provided by the steam mixed with the feed

-

it is favored by high temperatures and low pressure. We generally work at temperatures
on the order of 550°C to 650°C and at pressures below atmospheric pressure

-

it necessarily involves the use of a catalyst

b - Catalysts used
The catalysts used usually have five distinct elements:
-

an active base constituent (ferric oxide F e 0 3 )

-

a stabilizer (alumina: A l 0 3 ...)

-

a coke formation inhibitor (potassium oxide: K 0 )

-

a promoter (cupric oxide: CuO ...)
a binder that gives the system certain mechanical properties (calcium aluminate)

2

2

2

Although the catalytic formulae are generally selective, they cannot prevent certain side reactions.
Because of the temperatures involved, there is a tendency to coke formation, which is expected to be
delayed and minimized in the processes used.
c - Principle of process of styrene production by dehydrogenation of ethylbenzene
As indicated on appendix n°2, ethylbenzene is first vaporized by putting it in an exchanger and then
adding about 10% of the total quantity of steam needed for the transformation. This feed is then heated
to 530-550°C in an furnace and directed to the reactor.
The temperature of 600-650°C at which the dehydrogenation normally occurs is obtained by addition
of the remaining 90% of the water vapor brought to 800°C using the ethylbenzene pre-heating furnace.
The injection of this steam is done within the reactor. The steam /EB mass ratio of the feed is typically
between 1 and 2.

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

10

At the output of the reactor, the effluent temperature is close to 590 and 600°C, We then recover some
of these calories by feeding the effluent in an exchanger generating steam. The remainder is
dissipated in a cooling tower with prior on-line injection of the quench water.
The new units preferably include a series of reactors preceded by exchangers that make maintenance
work easier.
The cooling of the products leads to their partial condensation. Three phases appear:
-

a gaseous phase rich in hydrogen, carbon monoxide, carbon dioxide, light hydrocarbons
(methane, ethylene) to be used as fuel after treatment

-

an oily aqueous phase containing water and aromatics that we separate in a column

-

an organic phase composed mostly of styrene and ethylbenzene

This organic phase, plus the aromatics separated from the aqueous phase, is sent to a section for
separation by distillation shown in appendix n°3 and generally including four columns.
The first yields styrene at the bottom from a feed that initially contained on the order of 50% by weight.
This operation is very delicate because ethylbenzene and styrene have similar volatilities. This requires
working in a vacuum with injection of a polymerization inhibitor at the bottom because styrene
polymerizes easily.
The crude styrene is purified in a second column. It is obtained at the top and its final minimal purity is
from 99.7 to 99.8%. Before its sending for storage, we add a polymerization inhibitor of another type
that can react with the oxygen of the air, because oxygen can start the polymerization reaction in the
tanks.
The top effluent of the first column contains untransformed ethylbenzene, benzene, toluene and a little
styrene. It constitutes the feed for a third column where we obtain, at the top, benzene and toluene,
and at the bottom, the ethylbenzene that we recycle in the dehydrogenation reactor feed.
There can be an additional separation for benzene and toluene in order to recycle the benzene in the
alkylation unit.

00048_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

enspm
FORMATION INDUSTRIE
IFP

AICI3 ALKYLATION UNIT
— Typical operating conditions

TRAINING

BENZENE

<Z>

o

Flowrate (t/h)
Pressure (bar abs)
Temperature (°C)

© 2008 ENSPM Formation Industrie - IFP Training

+FURNACE

enspm
FORMATION INDUSTRIE
IFP

TRAINING

ETHYLBENZENE VACUUM DEHYDROGENATION
- Operating conditions -

( j - Figure 2 •
Pressure (abs bar)

Temperature (°C)

Fuel gas to vacuum system

STRIPPER

Steam
Ethylbenzene
recycling from
separation section

Ethylbenzene and styrene

© 2008 ENSPM Formation Industrie - IFP Training

enspm
FORMATION INDUSTRIE
IFP

TRAINING

Benzene to

DEHYDROGENATION EFFLUENT TREATMENT
— Operating conditions —

50

ALKYLATION

Benzene + toluene
20

• Figure 3 •
DEBENZENIZER
DETOLUENIZER

Temperature (°C)
Pressure (bar abs.)
Toluene

Ml

flBHI
PIS*
m

115

Ethylbenzene
to REACTOR

DEHYDROGENATION
VACUUM

140

DISTILLATION
COLUMN

50
T

_

6§ *

A

^

sTfJ-j^

15

;->
Y / / / / / / A

90

Polymerization inhibitors
(STORAGE)
STYRENE
PURIFICATION

Polymerization inhibitors
(DISTILLATION)

COLUMN
••

105
Heavies
© 2008 ENSPM Formation Industne - IFP Training

J

enspm

Refining-Petrochemicals-Chemicals-Engineering

ir P a T R A l N i N C i

VARIOUS PROCESSES
FOR MANUFACTURING POLYPROPYLENE

I

-

II -

FROM PROPYLENE TO POLYPROPYLENE

1

1 2 3 -

1
1
3

The economic importance of polypropylene
Characteristics of polypropylene - Relations between propetties and structure
Main compounds involved in the polymerization reaction

DEVELOPMENTS IN CATALYSTS AND MANUFACTURING P R O C E S S E S

3

1 -

Different generations of catalysts

4

2

-

Metallocene catalysis

5

3

-

Mam processes

9

PC P O L - 0 0 8 0 8 . B. A - R e v . O

05/06/2008
© 2008 ENSPM Formation Industrie - IFP Training

I

1

I-

FROM PROPYLENE TO POLYPROPYLENE
1 -

X~

T H E ECONOMIC IMPORTANCE O F P O L Y P R O P Y L E N E

,
y t•

Polypropylene (or more correctly polypropylenes, as there is now a wide and diversified range) is the
main outlet for propylene accounting for between 50 and 55% of the use of this olefin which itself has
an annual world production of nearly 50 million tons.
The importance of polypropylene has never ceased to grow since it first appeared. Among the large
tonnage plastics (commodity plastics) it is the one with the fastest growth. In forthcoming years its
annual growth rate should be of the order of 4 to 6%.

2 -

CHARACTERISTICS

OF

P O L Y P R O P Y L E N E - RELATIONS

BETWEEN

P R O P E R T I E S AND S T R U C T U R E
The variety of polypropylene currently being used has been manufactured industrially since the end of
the 1950s. Its development at the start of this decade was the result of the appearance of new
catalysts. These latter, first studied by K. Ziegler and then by G. Natta who applied the work of the
former to the polymerization of propylene, are commonly called Ziegler-Natta catalysts or ZN catalysts.
They have allowed the production of a material possessing very varied characteristics.
The main properties for which polypropylene owes its success are:
-

being relatively chemically inert

-

a good rigidity

-

a good resistance to scratching and abrasion

-

a good surface appearance, especially in the form of films

-

an absence of cracking under stress

-

interesting electrical insulating properties

-

a good impermeability to steam

The shock resistance properties have been improved to the extent that it can now be used for
manufacturing automobile bumpers.
The result is that polypropylene offers an excellent compromise between mechanical resistance,
lightness and appearance, whether it occurs in the form of a homopolymer (the propylene is then
the only monomer) or in the form of a copolymer, the comonomer usually being ethylene.
Most of these properties are closely related both to the length of the chains and to the partial
crystallinity of the polymer. This results from the stacking, which is affected by the manner in which the
propylene molecules align themselves with respect to one another within the macromolecules
manufactured. The relative position of a propylene chain with respect to another leads to three
possible configurations which are:

00808_B_A

-

the isotactic configuration

-

the syndiotactic configuration

-

the atactic configuration

© 2008 ENSPM Formation Industrie - IFP Training

2

Commercial polypropylene is of the isotactic variety, but this configuration is not however 100%
obtained. These configurations, where the atoms numbered from ® to © are in the same horizontal
plane, are shown below:
-

in the isotactic polymer, the methyl radical always occurs on the same side of the plane
CH

-

CH

3

CH

3

CH

3

3

in the syndiotactic polymer the methyl radical occurs alternately on one side or other of
the plane
CH

CH

3

CH
CH

CH

^

2

CH

CH

2

^
CH

3

3

CH

^

8

CH

CH

2

CH

2

3

in the atactic polymer, the methyl radical occurs at random on one side or other of the
plane
CH

_

.

CH

3

CH


CH

/

#

CH

3

CH

\

#
CH

2

/

©

CH

\

#
CH

2

/
2

CH

I
CH

3

\

#
CH

3

2

The table indicates the way in which some properties are altered depending on the majority
configuration.

00808_B_A

Isotactic

Syndiotactic

Atactic

Density

0.92-0.94

0.89-0.91

0.85 - 0.90

Melting point (°C)

165

135

Solubility in hydrocarbons
at20°C

insoluble

moderate

high

Rigidity

high

moderate

low

Percentage crystallinity

65%

© 2008 ENSPM Formation Industrie - IFP Training

3

3 -

MAIN C O M P O U N D S INVOLVED IN T H E POLYMERIZATION REACTION
To obtain the desired chain structure and chain length, in the polymerization reaction, a ZN catalyst
whose first role is to ensure that an isotactic configuration is produced is used on one hand, and
molecular hydrogen whose action and quantity can be used on the other hand to alter the mean chain
length.
The catalytic complexes that are used are produced by reacting titanium-based compounds that are
the catalysts with organo-aluminium compounds, which are the co-catalysts.
The two main tests used to ensure the quality of the final product are conducted on:
-

the proportion of isotactic polypropylene
the mean chain length that is estimated by the Melt Index

It goes without saying that this structural aspect has an influence on the material's applications and the
way that it can be used, which are in decreasing order of importance:
-

II -

injection 52%
extrusion 45%
blowing 1.3%
other transformation processes 1.4%

DEVELOPMENTS IN CATALYSTS AND MANUFACTURING PROCESSES
Developments in manufacturing processes have proceeded simultaneously with those catalysts whose
properties have been improved over the course of time. The desired properties are:
-

a high activity i.e. obtaining a high polymer productivity for a given quantity of catalyst
used. This is called the catalyst yield, the ratio of polymer produced to the weight of catalyst
used or the corresponding weight of elemental metal

-

a high selectivity characterized by the stereo specificity, i.e. the faculty to ensure the
production of an isotactic polymer and therefore to limit the atactic content

-

the final morphology of the polymer grains, i.e. a given shape and size that determines the
apparent density of the polymer and the flow properties of the grains formed

The evaluation of the catalytic formulation also involves the study of:
-

the sensitivity of the catalytic system with respect to the reagents regulating the length of
the chains that are called transfer agents and also possible catalyst poisons

-

the capacity of the catalytic system to favor copolymerization

All these characteristics are strongly related to the way the catalysts are prepared and their own nature.
For example since 1957, the start up date of the first polypropylene unit in the world, the changes brought to
catalytic formulations have not only resulted in lower cost manufacture but have also simplified the processes,
while meeting quality requirements of final consumers.

00808_B_A

© 2008 ENSPM Formation Industrie - IFP Training

4

1-

DIFFERENT GENERATIONS OF CATALYSTS
The table below provides a comparison of the performances of the different generations of catalysts.

Yield
Catalytic

Percentage

system

1

s t

(kgofPP

(kgofPP

per g cat)
slurry

per g cat)
mass

conditions

conditions

generation

isotacticity

Control of the

Requirements in terms

by weight

morphology

of the process

90-94

impossible

elimination of catalytic
residues and the

0.8-1.2

(end of 1950s)

atactic fraction

n d

2
generation
(early 1970s)
3

3-5

10-15

94-97

possible

5-10

15-30

90-95

possible

10-25

30-60

95-99

possible

25-35

70-120

95-99

possible

5000-9000

90-99

to confirm

elimination of catalytic
residues
elimination of the
atactic fraction

r d

generation
(late 1970s)
t n

4 generation
(early 1980s)
5

6

t n

generation
(late 1980s)
t h

generation

The first two generations were so called mass catalysts, the others up to the 5
were so-called supported catalysts and the 6
st

a - From the 1 to the 2

ncl

t h

t n

generation inclusive

generation is based on metallocene catalysis.

generation

The corresponding catalytic complex is in the form of microcrystals of titanium trichloride of a special
crystalline shape associated with an alkylaluminium, DEAC (diethylaluminium chloride). The difference
2

between the two generations is in the active area available that increased from 3 0 - 4 0 m / g to
2

150 m /g in the early 1970s thanks to research conducted by the company SOLVAY.

b - From the 3

r d

to the 5

The exploitation of the 3

t h

r d

generation
generation followed closely on that of the 2

n d

. The improvement of the

catalytic formulation resulted from an improved availability of titanium atoms by using an inorganic
support of magnesium dichloride (MgCl2) and the addition of supplementary compounds called
electron donors that were Lewis bases. The change between the different generations resulted from
the nature of these donors. The 5

t n

generation only used a single one added to the catalyst as soon as

it was manufactured, which in principle suppressed the need to store it and meter it at the
manufacturing site. This 5

t n

generation was created at the end of the 1980s and has only recently

come into general use.

00808_B_A

© 2008 ENSPM Formation Industrie - IFP Training

5

c - The 6

t h

generation

These are so-called metallocene catalysts that are completely different catalysts from the previous.
These are based on the elements zirconium (Zr) or hafnium (Hf) combined with methylaluminoxane
(MAO) which have extremely interesting properties and open enormous perspectives in terms of new
applications for entirely new materials with unprecedented properties.

2 -

METALLOCENE CATALYSIS
a - The various challenges encountered with polymer materials
In addition to the enormous economic challenge that polymer materials currently represent, there are
now those related to:
-

environmental aspects
the need to save energy at all stages in the life of polymers

-

recycling that has become desirable if not essential

To make the latter aspect more feasible, the ideal case is that manufactured articles should be made of
a single material. This is only possible if the plastics are ideally suited to each application.
Two solutions can therefore be envisaged:
-

create totally new polymers
improve the existing materials

This last solution has, using metallocene catalysis, become a major development line. Starting with a
reduced number of monomers (ethylene, propylene, styrene, etc.), it is already, and will be even more
in future, possible to produce an extremely diversified range of polymer materials including plastics and
elastomers.
Only a modification of the polymer structure can lead to the production of a material with new
properties.
Polyolefins are cheap and very widespread and on the whole can meet all the current economic and
environmental criteria. The replacement of some technical high added-value polymers by recyclable
and less expensive materials is underway.

b - Characteristics associated with certain catalysts - Consequences for the resulting material
• Catalyst stereospecificity

and activity • polymer morphology and

stereoregularity

A catalyst capable ensuring that a given structure is obtained is called stereospecific. This character
must be accompanied by a good activity, facilitating the start of polymerization.
The stereospecificity

of the catalyst leads to a stereoregular polymer with improved and

reproducible properties. These properties depend on the polymer morphology, which itself depends
on the polymer's stereoregularity.
Morphology here means the extent to w h i c h the polymer is either amorphous or crystalline. The
polymers chains have a greater organization, the more their structure is regular.

00808_B_A

© 2008 ENSPM Formation Industrie - IFP Training

6

For example so-called atactic polypropylene is characterized by an amorphous structure with no
regularity. It therefore has a soft, waxy consistency similar to that of paraffin, leading to a limited
industrial use.
Polypropylene is the type example of a material that has only become of value because of the
possibility of obtaining a stereoregular polymer. The stereoregular form obtained leads to a isotactic
polypropylene with a pronounced crystalline character that is very resistant, with a high melting point
and that is widely used both in the form of plastics and of fibres.
• The value and limits ofZN

catalysts

Until the industrial development of metallocene catalysts, only the catalysts developed in the 1950s by
K ZIEGLER and G NATTA were used for the production of stereoregular polymers.
Although these catalysts have been constantly improved in terms of activity and stereospecificity since
they were discovered, some combinations of olefins and some macromolecular structures are still
impossible to obtain by a ZN type catalytic system. These include polymers of cyclo-olefins,
syndiotactic polypropylene and syndiotactic polystyrene.
The structure of ZN catalysts is difficult to analyze so that there is insufficient knowledge of the
catalysis mechanism and especially an inability to vary the structure of these catalysts in a rational
manner. The studies that have been conducted have however shown that their structure has different
active sites whose distribution is not uniform. They are called multiple-site catalysts.
One site produces a polymer that differs from the neighboring site in terms of:
-

the molecular weight
tacticity
the co-monomer content

Some sites are inaccessible to monomers attached to long chains and can only act on the smallest
molecules.
The impossibility of demonstrating which site is involved in the various stages of polymerization leads
to the inability to change it or not knowing how to change it. This means that control of ZN catalysis is
difficult and, in certain cases, impossible.
c - The principle of metallocene catalysis
• The concept of chirality
Although metallocene catalysis was predicted by G NATTA in the 1950s, it was not until 1982 and the
works of Professor H BRINTZINGER that the theory formulated by G NATTA was confirmed and
validated, as were, certain postulates belonging to ZN catalytic systems.
The theory postulated that stereo specificity was related to the chirality of the active centre. The
chirality of a chemical compound is its possibility of existing in two forms whose structures are mirror
images of one another. A compound is said to be chiral if it cannot be superimposed on its mirror
image. If it is chiral, it has two enantiomers forms: one laevorotatory the other dextrorotatory. The two
forms have the same physical properties except for the way they deviate polarized light, which is
turned to the left by the first form and to the right by the second.
• The value of metallocenes
In contrast to ZN systems, the structure of metallocenes can be completely analyzed and changed at
will. They have a single active site accessible to the monomer with as consequence the production of
identical macromolecular chains associate with a resulting narrow Molecular Weight Distribution
(MWD).
00808_B_A

© 2008 ENSPM Formation Industrie - IFP Training

7

These two characteristics combined lead to excellent mechanical and optical properties in the resulting
polymer.
Metallocene catalysts provide independent control over:
-

theMWD

-

the tacticity

-

the distribution of co-monomers

i.e. final control of the properties of:
-

thermal resistance

-

shock resistance

-

transparency

-

hardness

of synthetic polymers (homopolymers and heteropolymers)
• History of metallocene

catalysis

The initial development of metallocene catalysis in homogeneous phase gave disappointing results.
Research was however restarted after the discovery that metallocenes could be activated by
methylaluminoxanes. On the basis of concepts belonging to heterogeneous catalysis, in the 1980s H
BRINTZINGER and J EWEN elucidated some aspects of the stereo specific polymerization resulting
from the use of these catalysts.
• Structure of metallocene

catalysts

Metallocenes are rigid chiral catalysts, consisting of a metallic core of titanium (Ti), zirconium (Zr) or
hafnium (Hf) sandwiched between unsaturated hydrocarbon rings such as cyclopentadiene or indene.
The rigidity of the molecule is ensured by hydrocarbon groups such as:

(-CH2-)

-

methyl

-

ethyl

-

isopropyl (CH3)2 C=)

-

dimethylsilyl S i ( C H )

(-CH2-CH2-)

3

2

However without the presence of a co-catalyst such as methylaluminoxane (MAO), an oligomer
consisting of a chain of aluminum (Al) atoms and oxygen ( 0 ) loosely bonded to methyl groups and
whose structure is still poorly known, these rigid chiral metallocene catalysts have little activity and do
not have a high isospecificity.
By making the complexing of the metallocenes more rigid, it seems that the resulting catalytic
combination becomes a stereorigid bridge complex, that is highly active producing an improvement of
the reaction kinetics.
It only requires a small quantity of metal (1 g for several tens of tons of PE) with, as a result, only a
small catalytic residue that does not alter the use of the polymers and the reliability of the products
manufactured.

00808_B_A

© 2008 ENSPM Formation Industrie - IFP Training

8

Such a catalyst is therefore stereospecific provided three conditions are met:
-

there is chirality necessary for the recognition of the reaction's orientation

-

there is steric fixation ensuring that the active site is accessible to the monomer molecules

-

there is rigidity guaranteeing constant reaction conditions throughout the growth of the
chain

d - Isotactic or syndiotactic insertions
• Isotactic

insertion

The principle of controlling isotactic insertion relies on the ability of the site to distinguish between the
two ways in which monomer can approach and which are ruled by steric factors.
A metallocene system is capable of orienting the first insertion correctly 90% of the time. At each
subsequent insertion, the monomer then finds itself in the same environment. The selectivity is,
however, greater because the start of the forced orientation of the chain influences the monomer's
coordination.
This coordination can reach 99% whereas the selectivity achieved by ZN catalytic system never
exceeds 98%. In general, the percentage of atactic segments polypropylene included in an isotactic
chain varies between 2 and 6%.
• Isotactic

insertion

The principle of controlling syndiotactic insertion relies on slightly different geometries and concepts. It
occurs with stereorigid complexes, whose geometry has a plane of symmetry with one face cluttered
and the other much more open.
This insertion can be conceived as the sum of two isospecific polymerizations in opposite directions. In
this case, all that has to be done is to disturb one side of the molecule to modify the nature of the
selectivity.
Full control over syndiotactic polymerization has yet to be achieved.
It is only since 1991 that polymers produced by metallocene catalysis have been available. Meanwhile
it seems that those catalysts are still quite expensive compared to Z.N. catalysts and their use is still
limited.

00808_B_A

© 2008 ENSPM Formation Industrie - IFP Training

9

3 -

T H E MAIN P R O C E S S E S
a - The original so-called S L U R R Y P R O C E S S
A diagram of the original S L U R R Y process is shown below.

Separation of PP
and diluent treatment

Drying
and melting

A

T T T
;

Atactic
polymers

r% nu n4

1
Catalyst
preparation

Heavy RecydedHC
diluent

'V.

' Reaction '

Separation C3- and
neutralization of catalytic complex

Separation
f water - HC
and centrifugation
0

Waste water
treatment

Recycled
* alcohol
• Water

Water treatment and recovery
of alcohol

This consisted of conducting the propylene polymerization in the presence of a heavy hydrocarbon
diluent, solvent of the monomer and of the atactic fraction, the isotactic polypropylene being insoluble.
The use of 1

s t

generation catalysts required a section for eliminating catalytic residues and a

section for processing the atactic fraction.
It is easy to see that the reaction zone was very small compared to the purification section.
The operating conditions in the reaction zone were a temperature of 60 to 80°C and a pressure of 5 to
15 bar. The slurry, formed of isotactic polypropylene in suspension in the hydrocarbon diluent
(usually hexane or heptane) also included the unreacted propylene and the atactic fraction which
was separated at the outlet of the reaction zone, in order to recycle the propylene.
The first processes used for manufacturing polypropylene were designed to accommodate the intrinsic
limitations of the Ziegler-Natta catalytic system then available.

00808_B_A

© 2008 ENSPM Formation Industrie - IFP Training

10

The flash distilled effluent was first injected with alcohol leading to the destruction of the catalyst
and was then injected with water, often containing sodium hydroxide, to neutralize it and to
remove catalytic residues (de-ashing) from the hydrocarbon phase.
The two phases were separated by decantation. The aqueous phase containing the alcohol was
sent to a distillation unit to recover the alcohol. The organic phase was centrifuged to separate
the diluent from the isotactic polymer. The unit's commercial product was then dried before
becoming available in the form of powder that was extruded.
The hydrocarbon diluent containing the soluble atactic fraction was purified before being recycled.
The purification involved eliminating not only the atactic fraction but also the water and alcohol
still present in the diluent because of their ability to poison the catalyst.
All this led to a high energy expenditure and a large waste water production requiring suitable
treatment.
The range of products manufactured was then limited to homopolymers of different Melt Index
obtained by varying the quantity of hydrogen injected into the reactor and copolymers containing
small quantities of co-monomers, usually of ethylene.
For technical and economic reasons, copolymers with a high concentration of co-monomer and
a high shock resistance could not be produced on this type unit.
The first major significant change to this process was the coming on line of 2
catalysts that no longer needed the section for eliminating the atactic fraction.

n d

generation

Both increasing environmental constraints and the first petroleum shock led to a significant
increase in the price of the monomer and of energy costs, so it became essential in the mid-1970s
to find a more efficient and cleaner process.
b - Current processes
The simplifications in terms of the process design, leading to a reduction in capital and
operating costs, was mainly the result of the coming on line of the so-called high-yield 4

th

generation of catalysts, with a high stereoregularity and controlled morphology. Taking
advantage of the properties of the new catalysts, these processes have a more diversified and
higher production, greater flexibility and are more environmentally friendly. All of these
considerations led producers to invest exclusively in these new processes from the mid-1980s.
For all of them, the simplifications involve;
-

the suppression of the stage of eliminating the catalytic residues (de-ashing)

-

the suppression of the section eliminating the atactic fraction

-

the suppression of the use of a hydrocarbon or mixture of hydrocarbons used as diluent
since these processes were able to produce polypropylene directly from propylene

As a general rule, the processes described below use the so-called of mass polymerization technique
i.e. by definition, the reaction is conducted in a reaction medium consisting only of monomer. This
latter can be:

00808_B_A

-

in the liquid state

-

in the gas state

© 2008 ENSPM Formation Industrie - IFP Training

11

There are two major types of process:
-

mass processes in liquid phase

-

mass processes in gas phase

which, in all cases, because of the high propylene concentration, provide a fast reaction rate,
c - Liquid-phase mass processes
These can be divided into:
-

loop reactor processes
continuous stirred tank reactor or CSTR processes

• Loop reactor

processes

One of the best-known processes in this class is the SPHERIPOL process whose licence was
originally held by MONTEDISON, but after mergers in recent years is now under the banner of
BASELL (a joint-venture of BASF-SHELL in polyolefin production).
• The SPHERIPOL

process

This principle of this process is shown in the diagram below.

Monomer flash and recycling

fe

^

Polymer degassing
, and catalyst de-activation ,,

Homopolymer

Copolymerization

or statistical copolymer

reactor

Drying

loop reactor with
circulator

The catalytic complex, the monomer, plus the hydrogen used as transfer agent are introduced into the
loop reactor. This manufactures grades of homopolymers and possibly statistical copolymers
containing less than 5% ethylene, this compound then being found in the load in the loop reactor.

00808_B_A

© 2008 ENSPM Formation Industrie - IFP Training

12

Above this ethylene content the polymer formed would be dissolved in the propylene. It should be
remembered that the homopolymer is insoluble in its own monomer and that the copolymers
manufactured at this stage must also remain insoluble. In this respect this process is sometimes called
the mass suspension process.
The operating conditions are a temperature of between 60 and 80°C and a pressure of between 35
and 50 bar.
Fouling is limited by the spherical shape of the catalyst and therefore of the granules coming out of the
reactor, by the narrow particle size distribution and by the high flow rate of the liquid in the loop
provided by a circulation pump integrated into the reactor. If polymer were to become dissolved in the
monomer this would increase the risk of fouling, which is also one of the reasons for which the
ethylene content in the reactor is limited.
The elimination of heat is facilitated by the reactor's design and by the great turbulence generated by
the circulation pump.
The reaction effluent is flash distilled at the exit of the loop reactor to recycle the unreacted propylene.
At this stage, it is possible to use the polymer obtained for producing shock-resistant copolymer. This
material requires the production of Ethylene-Propylene Rubber or EPR using the granules of
homopolymer. This cannot be done in the loop reactor because the rubber would dissolve in the
propylene carrying the polymer; it would not therefore become included in the granules and would tend
to foul up the loop reactor.
The manufacture of such a copolymer requires that the reaction be conducted in a second reactor
working in gas phase, or more precisely, in a fluidized bed reactor operating at a temperature of about
100°C and a pressure of about 15 bar.
In this case the process is called a hybrid process. The copolymer leaving the gas-phase reactor
enters in a low-pressure separator that removes residual monomer. As the catalyst is still active, the
polymer is then treated with steam to complete the stripping and ensure the neutralization of the
catalytic complex. The polymer is then fed into a drier operating by injection of nitrogen.
Other licence holders such as PHILLIPS, FINA and SOLVAY propose or have proposed processes
with loop reactors.
• Continuous stirred tank reactor

processes

These processes, also known as "liquid p o o l " processes, are derived from original REXALL
(REXENE/EL PASO) process that competed in the 1960s with the SLURRY process but were less
used although already operating at the time with propylene as reaction medium.
The most recent are:

00808_B_A

-

the EXXON-SUMITOMO process
the HYPOL process of MITSUI PETROCHEMICALS using the MONTEDISON/MITSUI
catalyst

-

the LIPPSHAC process using the SHAC SHELL catalyst

© 2008 ENSPM Formation Industrie - IFP Training

13

• The EXXON-SUMITOMO

process

This process for which a diagram of the principle is shown below is capable of manufacturing high
purity polymers.
Lights
Recycled liquid propylene

The stage that reduces the presence of low molecular weight polymer and of catalytic residues
consists of rinsing the reaction effluent with liquid propylene.
• The HYPOL process
As the diagram of the working principle below shows, this process is characterized by a set of stirred
reactors in series capable of producing the homopolymer and statistical copolymers and whose
flexibility can be increased by adding a fluidized bed gas-phase reactor for the production of shockresistant copolymers.

reaction section

00808_B_A

reaction section

recycling section

© 2008 ENSPM Formation Industrie - IFP Training

14

d - Gas-phase processes
Two types of process can be distinguished:
-

stirred reactors processes

-

fluidized bed reactor processes

• Stirred reactor gas-phase
* The NOVOLEN

processes

process

The pioneer process in this field was BASF's NOVOLEN process, dating from the end of 1960s,
competing with the SLURRY process but less used although operating without diluent.
Before the appearance of high-performance catalysts, the polymers manufactured on this type of unit
were of undistinguished quality because the unit did not have any section for eliminating the atactics
and catalytic residues.
t h

The appearance of 4 generation catalysts gave impetus to this process by removing its main
disadvantage. A diagram of the principle is given below.

Propylene recycling
from LP separator drum

Reaction section

Separation and extrusion sections

The initial choice of mechanical stirring resulted from the option of wanting to limit the recirculation of
gaseous propylene.
The addition of a second reactor in series increases the capacity of this type of unit and gives it more
flexibility. This was done at the end of the 1970s in order to produce shock-resistant copolymers.

00808_B_A

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15

* The AMOCO

process

As shown in the diagram of the principle below, this is a process based on a multi-stage, stirred
horizontal reactor.

Purge

Reaction and recycling sections

Degassing section

The polymer passes from one zone to another and the system behaves as if there were a series of
independent stirred reactors. This configuration results in a rather narrow overall residence time
distribution and hence a narrower particle size distribution of copolymer compared to that obtained with
a single stirred reactor.
It is also possible to alter the molecular weight distribution of the homopolymer by acting on the
hydrogen flow rate in the various zones.
As in other gas-phase processes, liquid propylene is injected to eliminate the heat of reaction. This
process appeared in the early 1980s for the manufacture of homopolymers.
The production of shock resistant copolymers started in the early 1990s with a unit of 135 000 tons per
year with two reactors. This development was made by AMOCO in association with the Japanese firm
CHISSO, this process is therefore also known as the AMOCO-CHISSO process.

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16

• Fluidized bed reactor processes
The pioneer in this field was the company UNION CARBIDE, which at the end of the 1960s developed
its UNIPOL process for the manufacture of high-density polyethylene HDPE, but it was only in 1985
that this process was adapted to polypropylene by using a SHELL SHAC catalyst.
This process includes a reactor dedicated to the production of homopolymers and statistical
copolymers and optionally a smaller reactor in series with the first, if shock resistant copolymers were
to be produced.
The circulation of the polymer by means of fluidization ensures a uniform production and favors the
removal of the heat of reaction by the gas forming the fluidized bed. The recycled gaseous propylene
can be cooled or even condensed.
In this case, when it is reintroduced into the reactor it increases the process's capacity to remove heat.
This technique is known as condensed mode operation.
The normal operating conditions are a temperature of about 65°C and a pressure of about of 30 bar.
The pressure in the reactor used for producing shock-resistant copolymers is about 20 bar. A diagram
of the principle of this unit is given below.

Downer column

00808_B_A

Riser column

© 2008 ENSPM Formation Industrie - IFP Training

17

• The SPHERIZONE

process

This process belonging to the company BASELL (BASF-SHELL) is designed for manufacturing two
different polypropylenes in the same reaction unit.
It consists of two columns. The propylene supply is fed into the top of the first one and flows from the
top to bottom. The introduction of a catalyst generates long chain polymers because of the low
hydrogen content in this so-called Downer c o l u m n . The gas and polymer leaving this column are
fed into the bottom of second Riser column.
Hydrogen is also fed into the bottom of this second column to help in the production of short chain
polymers. The gas, rich in hydrogen, and the polymer exit from the head of the column from where
they are fed back into the top of the first column, where a purge is conducted to remove the excess
hydrogen, whereas the polymer starts a new cycle. There is an average of 4 cycles, after which the
product is drawn off from the bottom of the first tower.
The polymer obtained is formed of various layers that are accumulated on the initial particles The
alternating short and long chains lead to an intimate, statistically very uniform, mixture. The principle of
the process is shown below.

Downer column

00808_B_A

Riser column

© 2008 ENSPM Formation Industrie - IFP Training

enspm
I'OMMAT ON I N C J M 1 1
i f P

w

T R A I N I N G

VARIOUS P O L Y E T H Y L E N E
MANUFACTURING P R O C E S S E S

I

-

II -

HIGH PRESSURE PROCESSES
1 -

Autoclave process

2

Tubular process

-

III -

1

2

LOW PRESSURE PROCESSES
1 2 -

1

Liquid phase processes
Gas phase processes

METALLOCENE-BASED CATALYSTS

© 2008 ENSPM Formation Industne - IFP Training

3

3

6

9

J

1

I-

HIGH PRESSURE PROCESSES
1-

AUTOCLAVE PROCESS
This was the first process in history to be used for manufacturing PE. The quality obtained is called
low-density polyethylene (LDPE). It was developed by ICI before the Second World War and the
license for this autoclave process has since been granted to many other companies.
The single or multiple stage reactor, generally fitted with a stirrer, is adiabatic i.e. it is neither directly
heated nor cooled. It is the monomer, at a mean temperature of 40°C, that absorbs the reaction heat
when it is introduced into the reactor. The working temperature is usually between 150 and 300°C, the
pressure between 1000 and 2500 bar. The conversion rate is limited to 15-20% for a residence time of
generally between 25 and 40 s. The initiator used for priming the reaction can be a peroxide, an
organic per-ester or a hydroperoxide.
A transfer agent is injected for regulating the chain length on certain grades.
This process can also be adapted to produce copolymers. In this case, it includes additional
equipment.
LP recycle

Purge

A ,

HPrecycle

0 1 1

* ^S>l
Oil

o--o

a--a
~5

Pre-compressor

C H - O

Hypercompressor

AUTOCLAVE

It can be considered to be a bulk polymerization.
The ethylene is compressed by two different multiple-stage compressors and cooled after each one
before being introduced into the reaction zone.
The polymer produced is in the molten state. On leaving the reactor, it is separated from the nonreacted ethylene in two successive HP and LP pressure separators.
The recycled HP ethylene, that accounts for most of the non-reacted ethylene, is sent back to the
suction of the HP compressor after having been cooled and having been rid of short chain polymers
that occur in the form of PE oil or grease.
The ethylene coming from the LP separator, after cooling and removing PE oils, is recirculated to the
suction of the pre-compressor where it is mixed with the ethylene supply.
The molten polymer coming out of the LP separator is fed directly into an extruder producing
commercial PE granules.

00810_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

2

2-

TUBULAR PROCESS
The other high-pressure process is the B A S F tubular process. The reactor consists of a tube several
hundred meters long (500 to 3000 m) arranged in a coil. It is heated then cooled by continuously
circulating water through a double wall around the reactor tube. Its outside diameter is about 200 mm
and the inside diameter varies from 70 to 80 mm. The working pressure is between 1200 and 3200 bar
and the working temperature is close to 300°C. The polymerization reaction is started by using oxygen
or other chemical initiators. The ethylene is compressed in successive stages and cooled after each
stage, then fed into the tubular reactor. Any transfer agent and/or the initiators) are added during the
last stage of compression or introduced along with the monomer into the reactor, or along the length of
the reactor.
Copolymers are also liable to be produced with this process. In this case, additional equipment is used.

LP recycle

Purge

HP recycle
Oil

S

Oil
Hypercompressor

Pre-compressor

C
C

Separators
Cooling water HP
LP
£

D
D

TUBULAR REACTOR

Extruder

Only the type of reactor differs between the autoclave process and the tubular process, the design of
the rest of the unit being almost the same. Compared to the autoclave reactor, the tubular reactor
operates over a wider temperature range and produces polymers whose molecular distributions are
also wider but with shorter branches.
The conversion rate is of the order of 20-30%, or even higher, for residence times of between 35-50 s.
It is mainly the capacity to cool the reaction medium that enables such rates to be obtained.
It should however be noted that the tubular process is more expensive to build and operate because of
the higher pressures.

00810_A_A

© 2008 ENSPM Formation Industrie - IFP Training

3

I! -

LOW PRESSURE P R O C E S S E S
High-density polyethylene (HDPE) appeared in the 1950s as the result of the discovery of two innovative
catalytic systems. These were firstly the so-called Ziegler-Natta catalysts based on transition metals such
as titanium and cobalt and secondly catalysts based on chromium oxide. By means of the latter, it became
possible to produce a new generation of PE under medium- or even low-pressure conditions. The range of
polyethylenes that could be produced was further increased in the 1970s with the introduction into the reaction
medium of so-called higher olefins such as butene-1, hexene-1 and octene-1, leading to the production of
linear low-density polyethylenes (LLDPE).
The processes used to produce HDPE were adapted so as produce LLDPE, which increased the flexibility of
the units.
Among the processes, two types can be distinguished, those working:
-

in liquid phase

-

in gas phase

LIQUID PHASE PROCESSES
When such a process is used, two distinct polymerization techniques are encountered leading to:
-

processes in solution

-

processes in a suspension or slurry

a - Process in solution
In this case, the ethylene, any co-monomer, the catalytic system and a hydrocarbon solvent capable of
dissolving the polymer formed are fed into the reactor. On leaving the reactor, the un-reacted ethylene
is flashed off before being recirculated to the reactor zone .
In order to inactivate the catalyst, an inactivation stage must be used. Then the solvent is in turn
separated from the polymer before being processed for re-use.
The PE in the molten state is sent to an extruder after a stage in which traces of solvent are removed
in a drier.
The diagram below shows a simplified layout of the various successive operations conducted in this
type of process.
Solvent recycle loop

Ethylene recycling
Compressor

REACTOR

'

.yw-iii'i

V>JW.HU'JtJit

y

00810_A_A

Dryer

Flash

Deactivating

Solvent

separator

drum

separator

© 2008 ENSPM Formation Industrie - IFP Training

4

Groups such as:
-

HOECHST

-

DSM

-

DOW

and others in time developed this type of technology.
'The HOECHST

Process

This company was among the pioneers of the Ziegler-Natta catalyst, starting its first unit in 1956. The
operating conditions used moderate temperatures of between 60 and 120°C and also moderate or
even low pressures, of the order of 10 to 60 bars.
• The DSM Compact Process
Since the 1960s, the Ziegler-Natta catalyst has been used in the DSM Compact Process. The solvent
in this case is a petroleum fraction. The stirred steel reactor is maintained at a temperature of about
130°C.
The catalyst is prepared in situ, i.e. in the reaction liquid itself.
The polyethylenes obtained have densities of between 0.93 and 0.97.
• The DOW Process
Although it only exists at sites currently or formerly owned by DOW, this in-solution process is widely
used throughout the world. The solvent in this case is a narrow petroleum fraction {CQ-CQ) and the
reaction zone consists of two stirred reactors in series. The average operating conditions are of the
order of 20 to 30 bars for the pressure and from 155 to 165°C for the temperature. The proportion of
polymer at the exit of the reaction zone is about 7 to 12% for a mean residence time of 30 minutes.
The pressure in the reaction effluent is decreased to about 2-3 bars to recuperate the unreacted
ethylene.
Finally we can mention the SCLAIR process of the company NOVA CHEMICALS working at a
moderate pressure and which is used by about a dozen companies in the world.
b - Processes in suspension or slurry
In this case, the ethylene, any comonomer, the catalytic system and a low boiling point hydrocarbon
not dissolving the polymer and used only as diluent to ensure correct heat dissipation, are fed into the
reaction zone. The most representative of these processes is the "Particle Form" (PF) process of the
company PHILLIPS PETROLEUM.
• The PHILLIPS PETROLEUM

Process

The reaction takes place in a tubular reactor forming a loop. The diluent in this case is usually
isobutane. The reaction mixture is maintained in liquid phase by using a pressure of the order of
30 bars at an operating temperature of between 70 and 110°C.
A suspension of solid polymer in liquid hydrocarbon forms that is called the "slurry" and which
circulates in the loop. The reaction mixture is drawn off semi-continuously through the decantation
legs. After this operation it is sent to a flash tank, where isobutane and unreacted monomers are
separated from the polymer.

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5

This is a flexible process, producing PE of variable characteristics. The catalyst having a very high
activity, the various reagents must be extremely pure. It is particularly suitable for preparing high
molecular weight products or copolymers (with propylene, butene-1, hexene-1) in a range of densities
from 0.925 to 0.962. Its simplicity and flexibility make it one of the most widely sold processes in the
United States.
This process was developed to replace the initial polymerization process in solution at low pressure
relying on the use of a catalyst based on chromium oxide on a solid support of aluminum silicate that
the American group, also a pioneer in the field, patented very early. Although it provides a very pure
product of excellent quality, the in-solution process has the disadvantage that it can only produce
polymers with a molecular weight of below 100 000 because above this the solubility in the
cyclohexane then becomes insufficient. Moreover, it is a process that requires a great deal of energy.
• The SOLVAY

Process

This process differs from the previous one in that it uses a Ziegler-Natta type catalyst. SOLVAY has
greatly contributed to the improvement of this catalyst, in particular by introducing catalysts supported
on magnesium chloride crystals, the base of the catalyst remaining identical, i.e. comprising a
transition metal compound such as titanium chloride activated by reaction with an organo-aluminum
compound.

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© 2008 ENSPM Formation Industrie - IFP Training

6

The polymerization is conducted in a loop reactor to which the various constituents are added.

• The BOREALIS Borstar Process
The major innovation in the last decade is the development of a suspension process in supercritical
mode belonging to the company BOREALIS.
Called the Borstar process, it produces polyethylene in the form of solid particles in supercritical
propane.
The reaction zone consists of a polymerization reactor, a reactor loop and a gas-phase reactor with a
fluidized bed.
The main advantages of the process include:
-

the lower solubility of PE in propane than in isobutane, which reduces the fouling of the
reactor and facilitates heat transfer

-

-

a lower heat consumption when separating the polymer from the diluent because of its high
volatility and with an improved separation quality
an improved hydrodynamic behavior (elimination of the risk of a water hammer when
drawing off the product and of cavitation in the pump)

-

00810JLA

the production of very low molecular weight polymers because of the absence of limits to
the introduction of hydrogen into the reaction medium

© 2008 ENSPM Formation Industrie - IFP Training

7

2-

GAS-PHASE PROCESSES
This technology appeared at the end of the 1970s and early 1980s. Since then, these processes have
been widely developed for the manufacture of LLDPE and HDPE.
a - The UNION CARBIDE Unipol Process
This process uses a vertical cylindrical reactor in which the gaseous ethylene and catalyst are
introduced continuously. A bed of polymer granules, fluidized by a circulating gas, flows through the
reactor from the bottom to the top. The structure is provided with a headspace dome or chamber at the
top to prevent the granules of polymer being carried away by the circulating gas. The gas consists of
monomer, of inert compounds with respect to the polymerization and hydrogen. It circulates by means
of a compressor situated on the recycling loop that also includes a heat exchanger to eliminate the
heat reaction contained in the gas, and even to ensure the condensation of hydrocarbons heavier than
n-hexane in the units in the so-called supercondensed mode. The cooled gas and the liquid that
appears are then re-injected into the base of the reactor that has an additional heat extraction sink
caused by the gasification of the liquid fraction.
This operational method has increased the production of existing units by almost entirely removing the
main constraint of gas-phase units, i.e. the ability to remove the heat of reaction.
The polymer, in powder form, is drawn off by means of system that alternately open and shuts the
discharge valve.

The joint venture between UC and EXXONMOBIL, called UNIVATION TECHNOLOGIES, currently
holds the patent for this process, of which there are currently at least 85 to 90 units.

00810_A_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

8

b - The L P Innovene Process
Shortly after Union Carbide, LP Chemicals brought into service its own fluidized bed gas-phase
process, called innovene, that was developed by its subsidiary Naphthachimie. As with the Unipol
process, this process is capable of producing various grades of LLDPE and HDPE.
The operating parameters are mild conditions (P = 20 bars, T = 75 to 110°C). As with the Unipol
process, it is adaptable to various catalytic systems, including chromium-based catalysts, Ziegler-Natta
and metallocenes. It works in a very similar way.
The polymer particles form within the fluidised bed reactor. The residence time is a few hours. The gas
at the reactor exit contains both monomers and co-monomers that have hydrogen and inert gases. All
the fine polymer particles swept away by the gas to the reactor exit are collected in a cyclone and
reintroduced into the reaction medium.
This design, unique to Innovene, eliminates the risk of blockage by growing polymer particles. The
circulating gas current composed of ethylene, co-monomer and hydrogen first passes through a heat
exchanger in which the heat energy given off by the reaction is removed. It is then compressed before
passing through another heat exchanger that condenses the liquid fraction; this fluid then goes through
a gas-liquid separator. The gas phase is introduced into the base of the reactor, whereas the liquid is
pumped and injected into the fluidized bed of reactor medium by means of a special nozzle. This is a
phase separation with separate injection of the liquid and gas that is the novelty of the socalled high-productivity L P process.

00810_A_A

© 2008 ENSPM Formation Industrie - IFP Training

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III -

METALLOCENE-BASED CATALYSTS
Figures 1 and 2 focus on the historical aspect of the development regarding the PEs technologies.
Figure 3 shows the two modes of catalyst used (Multi-Sites Catalyst MSC, Single-Site Catalyst SSC).
Metallocenes are the latest polymerization catalysts. The first industrial applications started in 1991 and
experts predict that an increasing proportion of polymer production will be obtained using metallocenes in
future years.
These are complex molecules consisting of a single metal atom bound to unsaturated C 5 cyclic hydrocarbons
or aromatic rings. These rings are connected to one another by various carbon chains that provide rigidity for
the whole structure. One of the main properties of the molecules is the absence of symmetry that gives them
geometrical properties that are very interesting in the polymerization of propylene and styrene. A second
catalytic agent is often used at the same time to activate the metallocene compound. The single active site of
these molecules is reproducible without too much difficulty, so that the catalyst is capable of producing very
uniform polymer molecules.
The main advantages of metallocene catalysis are:
-

a high polymerization yield. This enables very small quantities of catalyst to be used for
obtaining large quantities of polymer

-

a very strict control of the geometrical arrangement of the monomer molecules (socalled "steric control"). This is the case for the polypropylene and polystyrene, which gives
polymers with mechanical properties that would otherwise be unobtainable

-

the production of polymers molecules having very similar molar weights, i.e. having
almost the same number of monomer repeats. This gives the polymers special mechanical
and optical properties

-

the possibility of copolymerizing very diverse vinyl co-monomers with, in addition, a very
uniform distribution for these latter

The Ziegler-Natta catalyst has not however been abandoned and both technologies are now complementary.
Depending on demand, they provide a wide range of choices for the customer. A combination of these
technologies could also be envisaged to produce made-to-measure polymers.
Although the first industrial applications of metallocenes were used for polyethylene, they are now also used
for polypropylene.

00810_A_A

© 2008 ENSPM Formation Industrie - IFP Training

HP POLYETHYLENE P R O C E S S E S
— Figure 1

1930

1940

1950

1960

1970

1980

1990

- > LLDPE
• > LDPE

TUBULAR
Discovery

PROCESS"

s
Pilot
_ L _

1

Small
units

Medium
unite

High
productivity

Very high
productivity

5000 t/yr

25000 t/yr

units
60000 t/yr

units
100-300000 t/yr

Lab dev.
Commercial

AUTOCLAVE_

<

production

LAB
AUTOCLAVE A N D TUBULAR

TUBULAR PROCESS

PROCESS DEVELOPMENTS
PRODUCT DEVELOPMENT

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

"PROCESS"

enspm
FORMATION INDUSTRIE
IFP

TRAINING

LP POLYETHYLENE P R O C E S S E S

Metallocene

— Figure 2 —

Ziegler
complex
1950

1960

1970

1980

1990

Discoveries
Chromium
- > m HDPE or m LLDPE
- > LLDPE
- > HDPE

oxide
LINEAR PE

CHROMIUM
"OXIDE
CATALYSTS

Chromium
oxide
discovery

ZIEGLER

_Suspension - slurry

CATALYSTS

Ziegler
discovery

Gas phase

<
LAB
DEVELOPMENTS

CATALYSTS
PRODUCTS

© 2008 ENSPM Formation Industrie - IFP Training

enspm
FORMATION INDUSTRIE
IFP

TRAINING

SPECIFICITY OF METALLOCENE CATALYSIS

ZIEGLER-NATTA/PHILLIPS

• Figure 3

METALLOCENE

CATALYSTS

Short chains with
high incorporation rate

Medium chains
with medium
incorporation rate

Long chains with
low incorporation rate

MULTI-SITES CATALYST

MONO-SITE CATALYST

• Several active sites

• Single active site

- Different types of molecules with variable

• One type of molecules with steady comonomer

monomer incorporation rate

incorporation rate and a narrow regular weight distribution

CO

I

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

enspm
IFP

T R A I N I N G

ADDITION POLYMERIZATION
— Techniques and main characteristics —

I

-

II -

III -

POLYMERIZATION TECHNIQUES FOR ORGANIC MONOMERS

1

1 -

Exothermicity issue - Bulk and gas phase polymerization

1

2
3

Catalysts constraints - Solution and suspension polymerization in organic medium
Phases compatibility issues - Polymerization in aqueous phase (suspension - emulsion)

1
1

-

MAIN CHARACTERISTICS OF A COMMODITY PLASTICS

2

1 2 -

Measurement of fluidity
Fluidity as a function of chain length

2
4

3

Other characteristics

4

-

ELASTOMER VISCOSITY

5

05/06/2008

1

I-

POLYMERIZATION TECHNIQUES FOR ORGANIC MONOMERS
The technique implemented in a polymerization process depends on:
-

its ability to manage the considerable exothermicity usually involved in polymerization
reaction

1-

1

-

catalysts constraints

'

'

..

-

phases compatibility issues in the case of water used as a heat removal fluid

EXOTHERMICITY ISSUE - BULK AND GAS PHASE POLYMERIZATION
Polymerization reactions are most of the time very exothermic reactions. It is necessary to manage the
heat production within the process. That leads to the two following situations:
-

the monomer itself is able to remove the heat from the medium and is also used as a
transportation fluid. Bulk polymerization is implemented in that case (plates 1, 2, 3
p a r t i ) . Monomers, polymer and catalyst if needed only make up the medium, if the
monomer is in gas phase, that leads to a gas phase process

-

another fluid that of the monomer itself must be used as a heat removal fluid. Water seems
the first to be chosen

2 -

CATALYSTS CONSTRAINTS - SOLUTION AND SUSPENSION POLYMERIZATION
IN ORGANIC MEDIUM
Some catalysts can't stand water in liquid or vapour phase. An organic fluid is obviously needed to
solve the issue of the removal of heat. That leads to the two following situations:
-

the organic liquid is a solvent of the polymer. Hence, the technique implemented is the socalled solution polymerization technique (plate 3 part 2).

-

the organic liquid can't make soluble the polymer. It acts only as a diluent of the polymer.
Hence, the technique implemented is the so-called suspension polymerization technique
in organic medium or slurry technique

3 -

PHASES COMPATIBILITY ISSUES - POLYMERIZATION IN AQUEOUS PHASE
(SUSPENSION - EMULSION)
If water is chosen as the heat removal fluid of the medium, the issue is that water and organic
monomers can't be mixed together. They separate. It is necessary in such a case to disperse the
organic phase within the aqueous phase. Because, with respect to the polymerization reaction, the
medium simultaneously evolves, it is absolutely necessary to maintain this dispersed state.
Thanks to chemicals able to make compatible both aqueous and organic phase, such a result can be
obtained. According to the size of polymer particles, both techniques are implemented:
-

the so-called suspension technique in aqueous phase. Water, monomer, surfactants and
one or several organic soluble initiators make up the medium. Usually, the technique
implements a continuous stirred tank reactor. Polymer particles size finally is in the range of
0,1 to 5 mm in diameter. Plate 4 displays a PVC unit implementing this technique

-

the so-called emulsion technique in aqueous phase. Water,

monomer,

specific

surfactants and one or several water soluble initiators make up the medium. Usually, the
technique implements a continuous stirred tank reactor. Polymer particles size finally is
around 0,01 p m in diameter. That is 0,00001 mm
OO850_B_A

© 2008 ENSPM Formation Industrie - IFP Training

2

II -

MAIN CHARACTERISTICS OF A COMMODITY PLASTICS
Production of a commodity plastic is not sufficient itself, it is necessary that this plastic gets some specific
properties such as:
-

strength resistance
easy processability

Both requirements essentially depend on the average chain length that can be evaluated through out two
parameters:
-

the average degree of polymerization ( DP ) i.e. the average number of molecules of
monomer making up a macromolecule. Hence, for polypropylene, for instance, this number
ranges from 900 to 5000

-

the s o called Number Average Molecular Weight ( Mn ) written as:

Mn

=

DP

.Mo

Mo: molecular weight of monomer
Furthermore, it seems interesting to know about the extent of polymer heterogeneity. Actually, two sets of
macromolecules can get the same average degree of polymerization but to be made up with extremely
different chains in size.
More homogeneous the polymer, better its mechanical
polymerization.

resistance at a given average degree of

The parameter taking into account the heterogeneity is the so-called polydispersity factor (P). Its value is
always greater than 1, even if theoretically 1 could be reached as well. Closer this value to 1 more
homogeneous the polymer. For polypropylenes and with respect to applications, this parameter varies from 3
to 12.
Most of the time, the polydispersity of a polymer is the outcome of the process and the catalyst involved.

1-

MEASUREMENT OF FLUIDITY
At a given temperature, the fluidity of a polymer is characterized thanks to either the melt index or the
viscosity index
a - Melt index
By definition, the melt index corresponds to the quantity, in grams per ten minutes, of a melted polymer
flowing through out a calibrated restricted orifice at a given temperature and under a constant force.
The conditions of measurement are given by the ASTM 1238 Standard.

00850_B_A

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3

A simplified drawing of the experimental apparatus is shown hereunder.

Cylinder

Heating

— cylinder bore 9.5 to 10 mm in diameter
— die 2.09 to 2.10 mm in diameter

nsulator
Die carrier
Depending on the polymers, the conditions of the experiment are different, as displayed in the table
below. Thus, it's impossible to compare values in between different products.

Mass (kg)

Temperature (°C)

HDPE

2.16-5-21.6

190

LDPE

2.16

190

PS

5

200

PP

2.16-5

230

The melt index value must be taken into account when choosing the transformation technique (plate 5).
Thinner pieces, specially for molding applications, higher the fluidity of the polymer in order to be sure
that the total volume of the molding device is filled up with polymer.
b - Viscosity Index
Viscosity Index is used to characterized PVCs. A viscometer is needed. The measurements
correspond to the time taken first by a pure solvent and then the polymer made soluble in the solvent
to flow between two fixed marks.
Knowing both durations allows to establish the Viscosity Index that is a figure without dimension.

00850_B_A

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4

2-

FLUIDITY AS A FUNCTION OF CHAIN LENGTH
Generally speaking, longer the chains:
-

lower the Melt Index

-

higher the Viscosity Index

this points out a high viscosity leading to possible difficulties to transform the polymer.
In an opposite way, shorter the chains:
-

higher the Melt Index
lower the Viscosity Index

this points out a low viscosity leading to normally easier transformation capabilities of the polymer.

3-

OTHER CHARACTERISTICS
Other major characteristics are:
-

specific gravity

-

limit temperature of use
rigidity level
electrical properties

Traction modulus

Dielectric rigidity

(°C)

(MPa)

(kV/mm)

Limit temperature
Specific gravity

00850_B_A

of use

PS

1.05

- 7 0 to+75

3000-3300

55-70

HDPE

0.945-0.96

- 8 0 t o + 110

4 0 0 - 1 2 0 0 Vs Ml

45-50

LDPE

0.918-0.935

< + 80

200

50-70

PP

0.9

0to90

1200-1400

55-65

Rigid PVC

1.4

- 1 0 t o + 80

3500

80-100

Soft PVC

1.3

- 2 0 to 80

<3000

30-80

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

5

III-

ELASTOMER VISCOSITY
The MOONEY viscometer is composed of a chamber with streaked inside surface in which a streaked disc
runs driven by an electrical motor.

The sample is placed inside the chamber on both sides of the disc and heated up to 100 or 125°C.
For a motor at constant speed, resistant torque owing to the elastomer is as much high as it is 'consistent'. A
system, composed of a standard spring and of a comparator, measures this resistant torque. The result is a
figure known as the so-called Mooney viscosity.
100 units MOONEY correspond to a torque of 8.3 J or N.m.

00850_B_A

© 2 0 0 8 ENSPM Formation Industrie - IFP Training

-

© 2008 ENSPM Formation Industrie - IFP Training

Plate 1 -

enspm
FORMATION INDUSTRIE
IFP

TRAINING

S T Y R E N E BULK POLYMERIZATION

-

Plate 2

-

Styrene - Ethylbenzene Recycling

.

M

.

M

t

250

PELLETIZER

Thermal

110
Conversion rate
Temperature (°C)

165

135
11-15%

35-40%
REACTORS/

85 - 90%
>/

Pressure (bar abs.)
© 2008 ENSPM Formation Industrie - IFP Training

enspm
FORMATION INDUSTRIE
IFP

B

TRAINING

PRINCIPLE OF P R O P Y L E N E BULK UNIT
— Plate 3 —
Parti
Monomer recycling

POLYMER
MONOMER
SEPARATION
SECTION

PRINCIPLE OF POLYBUTADIENE SOLUTION UNIT

Part 2

Solvent recycling

Oxygenated
compounds

COAGULATION &
REACTION

CATALYST

SEPARATION

ZONE

DECOMPOSITION

HC SOLVENT/

ZONE

Water

SEPARATION
WATER/
POLYMER

© 2008 ENSPM Formation Industrie - IFP Training

POLYMER

enspm
FORMATION INDUSTRIE
IFP

TRAINING

PRINCIPLE OF A PVC UNIT

• Plate 4

COMPRESSOR

-

TO
GASOMETER

SETTLER

r

CONDENSER

32)

FRESH CVM
& RECYCLED )
'

r

BATCH PROCESS

CONTINUOUS PROCESS

© 2008 ENSPM Formation Industrie - IFP Training

FORMATION INDUSTRIE
IFP

B

T R A I N I N G

TRANSFORMATION P R O C E S S E S GUIDE
vs RESIN MELT INDEX

Figure n°5 —

0 0 8 5 0

B

- -

A

Transformation processes

Ml

Film and plastic sections

0.4 - 0.8

Injection molding common
and standard applications

4.0-12.0

Injection molding thin objects
and complex structure

35

© 2008 ENSPM Formation Industrie - IFP Training